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| United States Patent |
6,258,954
|
|
Kunimoto
, et al.
|
July 10, 2001
|
Fluorescent maleimides and uses thereof
Abstract
The present invention relates to compounds of formula I
##STR1##
provided that R.sub.1 and R.sub.2 not simultaneously stand for phenyl, the
use thereof in, for example, electroluminescent devices and as void
detection compounds.
| Inventors:
|
Kunimoto; Kazuhiko (Takatsuki, JP);
Otani; Junji (Kobe, JP);
Kodama; Kunihiko (Chitose, JP);
Yamamoto; Hiroshi (Takarazuka, JP);
Verhoustraeten; Patrick (Lorrach, DE);
Megert; Sonia (Ueken, CH);
Braig; Adalbert (Binzen, DE)
|
| Assignee:
|
Ciba Specialty Chemicals Corp. (Tarrytown, NY)
|
| Appl. No.:
|
643594 |
| Filed:
|
August 22, 2000 |
Foreign Application Priority Data
| Current U.S. Class: |
546/36; 546/256; 548/444; 548/524; 548/526; 548/549 |
| Intern'l Class: |
C07D 207/20; C07D 409/10; C07D 471/06 |
| Field of Search: |
548/549,526,524,444,527
546/36,256
|
References Cited
U.S. Patent Documents
| 3808434 | Apr., 1974 | Gutbier | 250/302.
|
| 4596867 | Jun., 1986 | Fields et al. | 534/799.
|
| 4985568 | Jan., 1991 | Lubowitz et al. | 548/431.
|
| 5151487 | Sep., 1992 | Lubowitz et al. | 528/170.
|
| 5496920 | Mar., 1996 | Pfaendner et al. | 528/487.
|
| Foreign Patent Documents |
| 0 456 609 | Nov., 1991 | EP.
| |
| 0 628 588 | Dec., 1994 | EP.
| |
Other References
Patent Abstracts of Japan #08231502 (Sep. 1996).
Patent Abstracts of Japan #08320582 (Dec. 1996),.
Patent Abstracts of Japan #09090442 (Apr. 1997).
Chem. Abst. JP-A2-50123664, (1974).
Tetrahedron vol. 51, No. 36 (1995) pp. 9941-9946.
Chem Pharm Bull. vol. 28 (7) (1980) pp. 2178-2184.
Chem Pharm Bull. vol. 37 (1989) pp. 2710-2712
J. Org. Chem. vol. 42, No. 17, (1977) pp. 2819-2825.
Appl. Phys. Lett. vol. 51 (12) 1987 pp. 913-915.
German Language publication pp. 2478-2486.
|
Primary Examiner: McKane; Joseph K.
Assistant Examiner: Wright; Sonya N.
Attorney, Agent or Firm: Crichton; David R.
Claims
What is claimed is:
1. A compound of formula I
##STR55##
wherein
R.sub.1 and R.sub.2 independently from each other stand for
##STR56##
wherein Q.sub.1 stands for hydrogen, halogen, phenyl, --E--C.sub.1 -C.sub.8
alkyl, --E-phenyl, wherein phenyl can be substituted up to three times
with C.sub.1 -C.sub.8 alkyl, halogen, C.sub.1 -C.sub.8 alkoxy,
diphenylamino, --CH.dbd.CH--Q.sub.2, wherein Q.sub.2 stands for phenyl,
pyridyl, or thiophenyl, which can be substituted up to three times for
C.sub.1 -C.sub.8 alkyl, halogen, C.sub.1 -C.sub.8 alkoxy, --CN, wherein E
stands for oxygen or sulfur, and wherein R.sub.21 stands for C.sub.1
-C.sub.8 alkyl, phenyl, which can be substituted up to three times with
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, or dimethylamino, and
R.sub.22 and R.sub.23 independently from each other stand for hydrogen,
R.sub.21, C.sub.1 -C.sub.8 alkoxy, dimethylamino,
or --NR.sub.4 R.sub.5, wherein R.sub.4 and R.sub.5, independently from each
other stand for hydrogen, phenyl, or C.sub.1 -C.sub.8 alkyl-carbonyl, or
--NR.sub.4 R.sub.5 stands for five- or six-membered ring system, and
R.sub.3 stands for allyl,
##STR57##
wherein Q.sub.3 stands for hydrogen, halogen, C.sub.1 -C.sub.8 alkoxy, or
C.sub.1 -C.sub.8 alkyl-phenylamido, unsubstituted or phenyl substituted
C.sub.1 -C.sub.8 alkyl, unsubstituted or substituted up to three times
with halogen, --NH.sub.2, --OH, or C.sub.1 -C.sub.8 alkyl,
and Z stands for a di- or trivalent radical selected from the group
consisting of substituted or unsubstituted cyclohexylene,
triazin-2,4,6-triyl, C.sub.1 -C.sub.6 alkylene, 1,5-naphthylene,
##STR58##
wherein
Z.sub.1, Z.sub.2 and Z.sub.3, independently from each other stand for
cyclohexylene or up to three times with C.sub.1 -C.sub.4 alkyl substituted
or unsubstituted phenylene,
and wherein R.sub.6 and R.sub.7, independently from each other, stand for
##STR59##
n stands for 1, 2 or 3, and m stands for 1 or 2, with the proviso, that
R.sub.1 and R.sub.2 not simultaneously stand for phenyl.
2. Process for the preparation of maleimides of the formula I according to
claim 1 by reacting a maleic anhydride with an amine, which comprises
using as maleic anhydride the diarylmaleic anhydride of the formula V
##STR60##
wherein R.sub.18 and R.sub.19, independently from each other stand for
R.sub.1 or R.sub.2 as defined in claim 1, and as amine the amine H.sub.2
N--R.sub.3 or the diamine H.sub.2 N--Z--NH.sub.2, wherein R.sub.3 and Z
are defined in claim 1.
3. A process for the preparation of maleimides I as set forth in claim 1,
which comprises reacting in a first step the diarylmaleic anhydride V as
set forth in claim 2 with ammonium acetate, then--in a second
step--reacting the thus obtained intermediate Vb
##STR61##
with a base, and in a third step reacting the obtained anion with a halogen
compound X--R.sub.3 or X--Z--X, wherein R.sub.3 and Z are defined as set
forth in claim 1, and X stands for halogen.
Description
The present invention relates to fluorescent maleimides of the formula I
##STR2##
wherein
R.sub.1 and R.sub.2 independently from each other stand for
##STR3##
wherein Q.sub.1 stands for hydrogen, halogen, phenyl, --E--C.sub.1 -C.sub.8
alkyl, --E-phenyl, wherein phenyl can be substituted up to three times
with C.sub.1 -C.sub.8 alkyl, halogen, C.sub.1 -C.sub.8 alkoxy,
diphenylamino, --CH.dbd.CH--Q.sub.2, wherein Q.sub.2 stands for phenyl,
pyridyl, or thiophenyl, which can be substituted up to three times with
C.sub.1 -C.sub.8 alkyl, halogen, C.sub.1 -C.sub.8 alkoxy, --CN, wherein E
stands for oxygen or sulfur, and wherein R.sub.21 stands for C.sub.1
-C.sub.8 alkyl, phenyl, which can be substituted up to three times with
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, or dimethylamino, and
R.sub.22 and R.sub.23 independently from each other stand for hydrogen,
R.sub.21, C.sub.1 -C.sub.8 alkoxy, or dimethylamino,
or --NR.sub.4 R.sub.5, wherein R.sub.4 and R.sub.5, independently from each
other stand for hydrogen, phenyl, or C.sub.1 -C.sub.8 alkyl-carbonyl, or
--NR.sub.4 R.sub.5 stands for a five- or six-membered ring system, and
R.sub.3 stands for allyl,
##STR4##
wherein Q.sub.3 stands for hydrogen, halogen, C.sub.1 -C.sub.8 alkoxy,
C.sub.1 -C.sub.8 alkyl-amido, unsubstituted or substituted C.sub.1
-C.sub.8 alkyl, unsubstituted or up to three times with halogen,
--NH.sub.2, --OH, or C.sub.1 -C.sub.8 alkyl substituted phenyl,
and Z stands for a di- or trivalent radical selected from the group
consisting of substituted or unsubstituted cyclohexylene, preferably
1,4-cyclohexylene, triazin-2,4,6-triyl, C.sub.1 -C.sub.6 alkylene,
1,5-naphthylene,
##STR5##
wherein
Z.sub.1, Z.sub.2 and Z.sub.3, independently from each other stand for
cyclohexylene or up to three times with C.sub.1 -C.sub.4 alkyl substituted
or unsubstituted phenylene, preferably unsubstituted or substituted
1,4-phenylene,
and wherein R.sub.6 and R.sub.7, independently from each other, stand for
##STR6##
n stands for 1, 2 or 3, and m stands for 1 or 2, with the proviso, that
R.sub.1 and R.sub.2 not simultaneously stand for phenyl,
and its different uses such as in electroluminescent devices and as void
detection compounds.
Compounds which are both, fluorescent and photostabile, are rare. This is
mainly because fluorescence and photostability are usually incompatible
with each other. The majority of fluorescent materials obtained to date
are compositions employing fluorescent dyes, showing advantages of strong
fluorescence, however, at the same time poor lightfastness, too. Hence,
the known fluorescent materials are applied for only limited applications,
e.g. interior uses, i.e. almost no uses are known for applications where
high lightfastness is required.
In particular, perylene based compounds (especially compounds of the known
LUMOGEN.RTM. series from BASF) for highly photostabile and fluorescent
compounds are used by dissolving it into media such as plastics to give
fluorescent compositions. However, their solubility is insufficient
thereby failing in obtaining strong color strength of the corresponding
compositions.
Further, EP-A 456,609 discloses the preparation and use of a
benzoimidazoisoindolone as a highly photostabile and fluorescent pigment.
However, this pigment exhibits only a weak solid-state fluorescence and a
weak reflection color. In addition, the obtained color range is limited to
only greenish yellow to yellow. Another disadvantage is that a kind of
benzoimidazoisoindolone irritates the skin and crystal growth is too fast
in a polymer matrix.
Also used are coumarin and rhodamine dyes dispersed in a plastic matrix
(so-called fluorescent pigments). However, their photostability is poor.
Some maleimide derivatives are well-known compounds. E.g. J.Org.Chem. 42
(1977) 2819-2825 describes 1,2-diphenylmaleyl derivatives such as
1,2-diphenylmaleyl-N-cyclohexylimide as a protecting group for amino
functions. Although it is mentioned that these compounds are yellow and
fluorescent, no examples and no evaluation is given with regard to
fluorescence properties and photostabilities.
Tetrahedron 51 (1995) 9941-9946 describe the synthesis of the marine
alkaloid polycitrin, another red, fluorescent 1,2-diphenylmaleyl
derivative, and intermediates thereof. However, the object of this work is
not to show ways to enhance fluorescent properties and photostability of
maleimide derivatives.
U.S. Pat. No. 4,596,867 describes the preparation of disubstituted maleic
anhydride compounds. On col. 5 it is speculated that the imides of this
compounds with amines such as t-butylaniline or octadecylamine can yield
soluble compounds useful as fluorescent dyes and markers. However, no
examples or other hints are given to support this statement. Rather,
examples are directed to the preparation of polyimides in which the
claimed anhydrides are reacted with diamines. In addition, there is no
teaching of how to increase the photostability of fluorescent maleimide
compounds.
Chem. Pharm. Bull. 28(7) (1980) 2178-2184 describes, too,
diphenylmaleimides of the formula
##STR7##
wherein R.sub.8 stands for --CH.sub.2 Ph, --CH.sub.2 CH.sub.2 CH.sub.3,
--CH(CH.sub.3).sub.2, and --CH.sub.2 CH(CH.sub.3).sub.2. Although the
compounds are described as yellow fluorescent compounds nothing is
mentioned concerning increasing the properties of photostability and
fluorescence.
JP-A2 50123664 describes a method for the preparation of
##STR8##
wherein R stands for C.sub.1 -C.sub.4 alkyl, phenyl or tolyl, and Ar stands
for phenyl or tolyl. Explicitly, two compounds are prepared wherein Ar
stands for phenyl, and R for n-butyl and phenyl, resp. However, nothing is
mentioned about fluorescence and photostability. Rather, it is speculated
that this compounds are usable as medical drugs, pesticides and starting
materials thereof.
Chem. Ber. 26 (1893) 2479 describes the preparation of
3,4,3',4'-tetraphenyl-1,1'ethandiyl-bis-pyrrole-2,5-dione. However,
nothing is known with regard to photostability, fluorescence, and its uses
inter alia in electroluminescent devices.
EP-A 628,588 describes the use of bismaleimides, especially
##STR9##
to increase the molecular weight of polyamides. However, no teaching is
given with regard to the photostability and fluorescence of the mentioned
compounds and other uses.
Hence, the object of the present invention was to provide photostabile
fluorescent compounds, preferably exhibiting a high photostability and a
strong solid-state and/or molecular state fluorescence. Further, another
object is to broaden the range of available colors within this field,
preferably strong reflection colors, combined with the abovementioned
properties.
In addition, the provided compounds should be usable in electroluminescent
devices as light-emitting substances, as void detection compounds, as inks
for security printings, emitters for scintilators, light absorbers for
solar collectors, light converters for agriculture etc.
Especially, fluorescent compounds should be provided which, compared to
optical brighteners, have a superior solubility thus making an
incorporation into paints and lacquers more easy. In addition, the
fluorescent compounds should show fluorescence in the solid state, a
superior photostability with no or only minimal products leading to
discoloration of e.g. white coatings, a lesser migration, a lesser
contamination of the working environment, fluorescence should be observed
only at voids and not at the whole surface yielding a better contrast
compared to e.g. optical brighteners and allowing the detection of minor
defects or damages. Further, the fluorescent compounds should be useful in
dark and white pigmented systems in which optical brighteners fail.
Finally, fluorescent compounds with a superior photostability should be
provided allowing long-term void detection, i.e. an inspection after
months or maybe years after the application.
Accordingly, the aforementioned fluorescent maleimides were found. In
addition, novel compounds, their preparation and uses of the provided
compounds such as in electroluminescent devices and as void detection
compounds were found, too.
A preferred embodiment of the present invention relates to fluorescent
maleimides of the formula II
##STR10##
wherein R.sub.9 has the meaning of R.sub.1, and R.sub.10 stands for
R.sub.3.
Another preferred embodiment of the present invention relates to
fluorescent maleimides of the formula III
##STR11##
wherein R.sub.11 stands for R.sub.1, and R.sub.12 stands for R.sub.2,
wherein R.sub.11 and R.sub.12 do no stand simultaneously for the same
substituent, R.sub.13 stands for R.sub.3.
Another preferred embodiment of the present invention relates to
fluorescent maleimides of the formula IV
##STR12##
wherein R.sub.13, R.sub.14, R.sub.16 and R.sub.17 independently from each
other stand for the radicals as defined under R.sub.1, and R.sub.15 stands
for a single bond, or a divalent radical, preferably selected from the
group consisting of substituted or unsubstituted cyclohexylen, preferably
1,4-cyclohexylene, C.sub.1 -C.sub.4 alkylene, 1,5-naphthylene,
##STR13##
particularly preferred R.sub.15 stands for a single bond,
2,5-di-tert.-butyl-1,4-phenylene, 1,2-ethylene, 1,5-naphthylene,
2,5-dimethyl-1,4-phenylene, 4,5-dimethyl-1,4-phenylene,
trans-1,4-cyclohexylene,
##STR14##
Particularly preferred inventive compounds are the following compounds:
##STR15##
##STR16##
C.sub.1 -C.sub.8 alkyl is typically linear or branched--where
possible--methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl,
isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,
n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl,
more preferably C.sub.1 -C.sub.4 alkyl such as typically methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.
C.sub.1 -C.sub.6 alkylene is typically methylene, 1,1-, 1,2-ethylene,
1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene.
C.sub.1 -C.sub.8 alkoxy is typically methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy,
2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy,
1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C.sub.1 -C.sub.4
alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
sec.-butoxy, isobutoxy, tert.-butoxy.
Halogen stands for fluoro, chloro, bromo or iodo, preferably for chloro or
bromo.
C.sub.1 -C.sub.8 alkyl-carbonyl is typically methyl-carbonyl (=acetyl),
ethyl-carbonyl, n-propyl-carbonyl, isopropyl-carbonyl, n-butyl-carbonyl,
sec.-butyl-carbonyl, isobutyl-carbonyl, tert.-butyl-carbonyl,
n-pentyl-carbonyl, 2-pentyl-carbonyl, 3-pentyl-carbonyl,
2,2-dimethylpropyl-carbonyl, n-hexyl-carbonyl, n-heptyl-carbonyl,
n-octyl-carbonyl, 1,1,3,3-tetramethylbutyl-carbonyl and
2-ethylhexyl-carbonyl, more preferably C.sub.1 -C.sub.4 alkyl-carbonyl
such as typically methyl-carbonyl, ethyl-carbonyl, n-propyl-carbonyl,
isopropyl-carbonyl, n-butyl-carbonyl, sec.-butyl-carbonyl,
isobutyl-carbonyl, tert.-butyl-carbonyl.
C.sub.1 -C.sub.8 alkyl-amido is typically acetamido, ethaneamido,
n-propaneamido, isopropaneamido, n-butane-amido, sec.-butane-amido,
isobutane-amido, tert.-butane-amido, n-pentane-amido, 2-pentane-amido,
3-pentane-amido, 2,2-dimethylpropane-amido, n-hexane-amido,
n-heptane-amido, n-octane-amido, 1,1,3,3-tetramethylbutane-amido and
2-ethylhexane-amido, more preferably C.sub.1 -C.sub.4 alkane-amido such as
typically acetamido, ethaneamido, n-propaneamido, isopropaneamido,
n-butaneamido, sec.-butaneamido, isobutaneamido, tert.-butaneamido.
If --NR.sub.4 R.sub.5 stand for a five- or six-membered ring system, the
following ring systems are preferred: 4-morpholinyl
(=morpholino),1-indolinyl, 1- or 2-piperidyl, 1-piperazinyl, 1-indolinyl,
2-isoindolinyl, 1-quinuclidinyl, 1-pyrrolidinyl, and 9-carbazolyl.
The inventive maleyl derivatives I to IV can be synthesized starting from
the corresponding maleic anhydrides and amines in analogy to methods well
known in the art such as described in Tetrahedron Letters 31(36) (1990)
5201-5204, J.Org.Chem. 42 (17) (1977) 2819-2825, Chem. Pharm. Bull. 28(7)
(1980) 2178-2184, or by methods described in Tetrahedron 51(36) (1995)
9941-9946 or JP-A2 50123664.
In a preferred embodiment the corresponding diarylmaleic anhydride of the
formula V
##STR17##
wherein R.sub.18 and R.sub.19, independently from each other stand for
R.sub.1 or R.sub.2, is reacted with an amine H.sub.2 N--R.sub.3 or diamine
H.sub.2 N--Z--NH.sub.2.
The corresponding maleic anhydrides are known or can be prepared in analogy
to known methods e.g. as described in J.Org.Chem. 55 (1990) 5165-5170 or
U.S. Pat. No. 4,596,867, or as described in detail below. Amines H.sub.2
N--R.sub.3 and diamines H.sub.2 N--Z--NH.sub.2 are also known and
commercially available from chemical suppliers.
Usually the molar ratio of anhydride V to amine H.sub.2 N--R.sub.3 is
chosen in the range of from 0.1:1 to 2:1. Usually the molar ratio of
anhydride V to diamine H.sub.2 N--Z--NH.sub.2 is chosen in the range of
from 0.5:1 to 5:1.
Preferably, the reaction is carried out in the presence of a solvent,
wherein the amount of solvent usually is chosen in the range of from 5 to
50 weight-%, related to the diarylmaleic anhydride V.
As solvents usual organic solvents such as acetic acid, toluene,
dimethylformamide or a mixture thereof can be chosen.
The reaction temperature preferably is chosen in the range of from 80 to
150, more preferred from 100 to 120.degree. C.
The reaction time--usually depending from the chosen reaction
temperature--preferably is chosen in the range of from 2 to 20 hours.
After removal of the solvent, the product can be purified by known methods
if desired, e.g. by chromatography, or crystallization.
If so-called unsymmetrical maleimides I or IV are desired, i.e. R.sub.3
stands for e.g.
##STR18##
wherein R.sub.6 and R.sub.7 stand for a substituent as described for
R.sub.1 and R.sub.2, but are different from the chosen R.sub.1 and
R.sub.2, or in formula IV R.sub.13 and R.sub.14 are different from
R.sub.16 and R.sub.17, then it is preferred to add small amounts of
anhydride V to a surplus of diamine H.sub.2 N--Z--NH.sub.2, isolate the
obtained product Va
##STR19##
and react this amine Va with another anhydride V, in which the aryl
substituents, e.g. R.sub.6 and R.sub.7 or R.sub.16 or R.sub.17, are chosen
differently from R.sub.18 and R.sub.19. Of course other possibilities
shall not be excluded, e.g. if one amino group of the diamine is protected
etc.
Another preferred embodiment relates to a process for the preparation of
maleimides I, wherein in a first step the diarylmaleic anhydride V is
reacted with ammonium acetate to yield the intermediate Vb
##STR20##
Intermediate Vb then is reacted with a base, and the obtained anion in a
subsequent step with a halogen compound X--R.sub.3 or X--Z--X to yield a
desired product according to formula I.
Usually, the molar ratio of diarylmaleic anhydride V to ammonium acetate is
chosen in the range of from 0.01:1 to 0.5:1, preferably from 0.05:1 to
0.15:1.
Preferably, the reaction temperature is chosen in the range of from 80 to
130.degree. C., more preferably under reflux conditions of the reaction
mixture. It is preferred, too, to carry out the reaction in a solvent. The
amount of solvent preferably is chosen in the range of from 10 to 100
weight-%, related to the amount of diarylmaleic anhydride V.
As solvent usual organic solvents such as toluene, DMF, or a mixture
thereof, or acetic acid, preferably acetic acid can be used.
Generally, the reaction time is chosen in the range of from three to 20
hours.
The desired intermediate Vb can be worked up in usual ways such as
filtering, washing, and--if desired--further purification by
chromatography.
The molar ratio of the base and intermediate Vb preferably is chosen in the
range of from 1:1 to 5:1.
As a base an alkali metal alkoxide, an alkali metal hydride such as
potassium tert.-butoxide, sodium hydride or potassium hydride, preferably
sodium hydride, can be used.
Preferably, the reaction with the base is carried out in the presence of a
solvent. The amount of solvent can be chosen in the range of from 5 to 100
weight-%, related to intermediate Vb. As solvent usual organic solvents
such as N-methylpyrrolidone ("NMP"), or dimethyl formamide ("DMF"),
preferably DMF, can be used.
The reaction temperature usually is chosen in the range of from 20 to
80.degree. C., preferably room temperature.
The reaction time usually is chosen in the range of from 0.5 to 5 hours.
Preferably, the reaction mixture is not worked up.
Then, halogen compound X--R.sub.3 or X--Z--X is added to the obtained
reaction mixture. Usually, the molar ratio of X--R.sub.3 or X--Z--X to
intermediate Vb is chosen in the range of from 1:1 to 10:1.
The reaction temperature usually is chosen in the range of from 20 to
120.degree. C., preferably room temperature.
The reaction time usually is chosen in the range of from 0.5 to 10 hours.
After adding water to the reaction mixture, usually 0.5 to 10 times in
volume related to the amount of solvent, if desired, the obtained
diarylmaleimide can be worked up in usual ways such as extraction and/or
chromatography.
Another preferred embodiment relates to a process for the preparation of
diarylmaleic anhydrides V in which a glyoxylic acid derivative VI
##STR21##
is treated with a base and, subsequently, the thus obtained salt VIa is
reacted with a carboxylic acid VII
##STR22##
wherein (a) R.sub.18 stands for R.sub.1 and R.sub.19 for R.sub.1 or
R.sub.2, or (b) R.sub.18 stand for R.sub.2 and R.sub.19 R.sub.1.
Usually, the molar ratio of the base to glyoxylic acid derivative VI is
chosen in the range of from 1:1 to 20:1, preferably from 1.5:1 to 3:1.
As a rule, the temperature during the formation of the salt VIa is chosen
in the range of from 50 to 110, preferably from 70 to 80.degree. C.
Preferably, the salt-formation of VIa is carried out in the presence of an
aliphatic alcohol such as C.sub.1 -C.sub.4 alkanols such as methanol,
ethanol, n-, i-propanol, n-, iso-, sek.-, tert.-butanol. The amount of
solvent usually is chosen in the range of from 3 to 100, based on the
amount of glyoxylic acid derivative VI.
As a base preferably alkoxides such as alkali metal alkoxides, more
preferably alkali metal salts of C.sub.1 -C.sub.4 alkanols such as sodium
methanoate, potassium methanoate, sodium acetate, potassium acetate,
sodium n-propanoate, potassium n-propanoate, sodium n-, iso-, sek.-, tert.
butanoate, potassium n-, iso-, sek.-, tert.-butanoate, preferably
potassium tert.-butanoate, can be used.
Usually, the reaction time is chosen in the range of from 0.5 to 5 hours.
As a rule, the obtained salt VIa is separated from the reaction mixture,
preferably followed by removal of the solvent and drying over in an
atmosphere under reduced pressure.
In the second step of the above process the salt VIa is mixed with the
carboxylic acid VII usually in the presence of acetic anhydride at a
temperature in the range of from 80 to 140.degree. C., preferably under
reflux conditions of the reaction mixture.
In general, the molar ratio of glyoxylic acid salt derivative VIa to
carboxylic acid VII is chosen preferably in the range of from 5:1 to
0.2:1, preferably from 0.8:1 to 1.2:1.
Generally, the amount of acetic anhydride to the amount of glyoxylic acid
salt derivative VIa is chosen preferably in the range of from 0.05:1 to
1:1, preferably from 0.1:1 to 0.2:1.
Usually, the reaction time of this second step is chosen in the range of
from 0.5 to 10, preferably from one to three hours. The isolation of the
product can be carried out by known methods in the art, e.g. removing of
acetic anhydride by distillation, preferably under an atmosphere of
reduced pressure, followed by washing the product with appropriate organic
solvents such as acetone or ethyl acetate or by crystallization or
chromatography etc.
The carboxylic acid VII can be obtained by reducing the glyoxylic acid
derivative VI with a reducing agent such as hydrazine under basic
conditions.
In a preferred embodiment the glyoxylic acid derivative VI is treated with
hydrazine or hydrazine monohydrate in a temperature range of from 70 to
120.degree. C., preferably under reflux conditions, usually for 0.2 to 2
hours. Thereafter, a base such as a alkali metal or earth alkaline metal
hydroxide such as sodium hydroxide or potassium hydroxide is added to the
reaction mixture after cooling down to a temperature in the range of from
80 to 100, preferably from 95 to 100.degree. C., and then heated to a
temperature range of from 100 to 120.degree. C., preferably under reflux
conditions for 2 to 10 hours. Afterwards, the hydrazine is removed e.g. by
distillation, and the thus obtained reaction mixture preferably is
acidified with a mineral acid such as hydrochloric acid, sulfuric acid,
nitric acid, preferably hydrochloric acid, to a pH in the range of from 2
to 4. After that the product can be isolated e.g. by extraction with an
appropriate solvent such as methylene chloride, followed e.g. by
crystallization or column chromatography.
The molar ratio of hydrazine to glyoxylic acid derivative VI usually is
chosen in the range of from 2:1 to 20:1, preferably from 5:1 to 10:1.
The amount of the base usually is chosen in the range of from 2 to 10,
preferably from 3 to 5 weight-%, related to glyoxylic acid derivative VI.
The glyoxylic acid derivative VI can be obtained by saponification of ester
VIII
##STR23##
wherein R.sub.20 stands for C.sub.1 -C.sub.4 alkyl, in analogy to known
methods.
Preferably, ester VII is treated with a base such as an alkali metal
hydroxide, preferably sodium hydroxide, potassium hydroxide, and the like
in the presence of a polar solvent such as an C.sub.1 -C.sub.4 alkanol or
an aqueous solution thereof. In a preferred embodiment the saponification
is carried out in the presence of a mixture of water and an alkanol
R.sub.20 OH in a volume ratio of 5:1 to 0.5:1. Further it is preferred to
carry out the saponification at an elevated temperature, such as in the
range of from 70 to 100.degree. C., preferably under reflux conditions at
ambient pressure.
The reaction time mainly depends on the reactivity of the educts and the
chosen temperature. E.g. under reflux conditions the reaction time usually
is chosen in the range of from one five hours.
After that, the reaction mixture usually is acidified with an acid to a pH
range of from 2 to 4. As an acid mineral acids such as hydrochloric acid,
sulfuric acid and nitric acid, preferably hydrochloric acid, can be used.
Generally, the desired glyoxylic acid derivative VII is isolated from the
reaction mixture by known methods such as extraction, crystallization,
chromatography, preferably extraction.
The starting material, ester VIII, can be prepared by treating the aryl
compound with the halogen glyoxylate X
##STR24##
wherein X stands for a halogen, preferably for chlorine or bromine, in the
presence of AIX.sub.3 and a solvent.
In a preferred embodiment, a mixture of AIX.sub.3 in a solvent such as
methylene chloride is added portionwise, preferably dropwise, to a mixture
of compounds IX and X.
Usually, the molar ratio of aryl compound IX to halogen glyoxylate X is
chosen in the range of from 0.5:1 to 5:1, preferably from 0.8:1 to 2:1.
The amount of AIX.sub.3 preferably is chosen in the range of from 1 to 2
weight-%, related to the amount of glyoxylate X.
During the addition of AIX.sub.3 to the mixture of compound IX and
glyoxylate X, the reaction temperature is chosen preferably in the range
of from -10 to 20, more preferably from 0 to 5.degree. C. After the
addition the reaction temperature usually is chosen in the range of from
10 to 40.degree. C., the preferred temperature is room temperature.
The reaction time generally is in the range of from 3 to 20 hours.
Thereafter, the reaction mixture preferably is treated with water,
preferably ice and acidified to a pH in the range of from 2 to 4 with one
of the above mentioned mineral acids, preferably diluted hydrochloric
acid. The isolation of he product can be carried out with methods well
known in the art such as extraction with dichloromethane or diethylether.
If desired the ester II can be further purified e.g. by chromatography.
Other compounds such as the intermediate
##STR25##
can be prepared in analogy to the abovementioned process.
Another embodiment of the present invention relates to the use of the
claimed maleimides as well for all other fluorescent maleimides according
to the general formula given in this application or mentioned in the
examples for scintillator films for the detection of atomic and nuclear
radiation. In their simplest form these detectors usually consist of a
polymer matrix, such as polystyrene, containing low concentrations of a
fluorescent maleimide as fluorophore or an energy donor/acceptor mixture
containing a fluorescent maleimide as a key component.
Another embodiment of the present invention relates to the use of the
claimed fluorescent maleimides or those known compounds mentioned
additionally in the examples for the preparation and use of luminescent
solar energy collectors. The operation of a luminescent solar concentrator
usually is based on the absorption of solar radiation in a collector
containing a fluorescent species in which the emission bands have little
or no overlap with the absorption bands. Generally, the fluorescence
emission is trapped by total internal reflection and concentrated at the
edges of a collector, which is usually a thin flat plate, to the edge of
which a p-n junction photovoltaic ribbon is fixed and the light energy
converted to electrical energy. Luminescent solar collectors usually can
collect both direct and diffuse light, and there is a good heat
dissipation of non-utilized energy. Tracking of the sun usually is
unnecessary and fluorescent species can be selected to allow matching if
the concentrated light to the maximum sensitivity of the photovoltaic
cell.
A further embodiment of this invention relates to the use of the claimed
fluorescent maleimides or those known compounds mentioned additionally in
the examples for the preparation and use of printing inks such as gravure,
flexo and off-set inks preferably for publication, packagings and
laminations, as well as non-impact printings such as ink jet printing inks
and electrophotographic toners for printers and copy machines. The
maleimides can be applied in the usual method known in the art. The inks
can be used also in a way known in the art for functional inks as well as
for security printings for banknotes and indicators.
Another embodiment of the present invention is related to a method of
coloring high molecular organic materials (having a molecular weight
usually in the range of from 10.sup.3 to 10.sup.7 g/mol) by incorporating
the inventive fluorescent compounds by known methods in the art.
As high molecular weight organic materials the following can be used such
as biopolymers, and plastic materials, including fibers.
The present invention relates preferably to the use of the inventive
maleimides I for the preparation of
inks, for printing inks in printing processes, for flexographic printing,
screen printing, packaging printing, security ink printing, intaglio
printing or offset printing, for pre-press stages and for textile
printing, for office, home applications or graphics applications, such as
for paper goods, for example, for ballpoint pens, felt tips, fiber tips,
card, wood, (wood) stains, metal, inking pads or inks for impact printing
processes (with impact-pressure ink ribbons), for the preparation of
colorants, for coating materials, for industrial or commercial use, for
textile decoration and industrial marking, for roller coatings or powder
coatings or for automotive finishes, for high-solids (low-solvent),
water-containing or metallic coating materials or for pigmented
formulations for aqueous paints, for the preparation of
pigmented plastics for coatings, fibers, platters or mold carriers, for the
preparation of
non-impact-printing material for digital printing, for the thermal wax
transfer printing process, the ink jet printing process or for the thermal
transfer printing process, and also for the preparation of
color filters, especially for visible light in the range from 400 to 700
nm, for liquid-crystal displays (LCDs) or charge combined devices (CCDs)
or for the preparation of cosmetics or for the preparation of
polymeric ink particles, toners, dry copy toners liquid copy toners, or
electrophotographic toners, and electroluminescent devices.
Illustrative examples of suitable organic materials of high molecular
weight which can be colored with the inventive fluorescent maleimides of
this invention are vinyl polymers, for example polystyrene,
poly-.alpha.-methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene,
poly-p-hydroxyphenylstyrene, polymethyl methacrylate and polyacrylamide as
well as the corresponding methacrylic compounds, polymethylmaleate,
polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinyl
fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl
acetate, polymethyl vinyl ether and polybutyl vinyl ether; polymers which
are derived from maleinimide and/or maleic anhydride, such as copolymers
of maleic anhydride with styrene; polyvinyl pyrrolidone; ABS; ASA;
polyamides; polyimides; polyamidimides; polysulfones; polyether sulfones;
polyphenylene oxides; polyurethanes; polyureas; polycarbonates;
polyarylenes; polyarylene sulfides; polyepoxides; polyolefins such as
polyethylene and polypropylene; polyalkadienes; biopolymers and the
derivatives thereof e.g. cellulose, cellulose ethers and esters such as
ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate,
starch, chitin, chitosan, gelatin, zein; natural resins; synthetic resins
such as alkyd resins, acrylic resins, phenolic resins, epoxide resins,
aminoformaldehyde resins such as urea/formaldehyde resins and
melamine/formaldehyde resin; vulcanized rubber; casein; silicone and
silicone resins; rubber, chlorinated rubber; and also polymers which are
used, for example, as binders in paint systems, such as novolaks which are
derived from C.sub.1 -C.sub.6 -aldehydes such as formaldehyde and
acetaldehyde and a binuclear or mononuclear, preferably mononuclear,
phenol which, if desired, is substituted by one or two C.sub.1 -C.sub.9
alkyl groups, one or two halogen atoms or one phenyl ring, such as o-, m-
or p-cresol, xylene, p-tert.-butylphenol, o-, m- or p-nonylphenol,
p-chlorophenol or p-phenylphenol, or a compound having more than one
phenolic group such as resorcinol, bis(4-hydroxyphenyl)methane or
2,2-bis(4-hydroxyphenyl)propane; as well as suitable mixtures of said
materials.
Particularly preferred high molecular weight organic materials, in
particular for the preparation of a paint system, a printing ink or ink,
are, for example, cellulose ethers and esters, e.g. ethylcellulose,
nitrocellulose, cellulose acetate and cellulose butyrate, natural resins
or synthetic resins (polymerization or condensation resins) such as
aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde
resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins,
polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyester,
ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and
silicone resins as well as their possible mixtures with one another.
It is also possible to use high molecular weight organic materials in
dissolved form as film formers, for example boiled linseed oil,
nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and
urea/formaldehyde resins as well as acrylic resins.
Said high molecular weight organic materials may be obtained singly or in
admixture, for example in the form of granules, plastic materials, melts
or in the form of solutions, in particular for the preparation of spinning
solutions, paint systems, coating materials, inks or printing inks.
In a particularly preferred embodiment of this invention, the inventive
fluorescent maleimides I are used for the mass coloration of polyvinyl
chloride, polyamides and, especially, polyolefins such as polyethylene and
polypropylene as well as for the preparation of paint systems, including
powder coatings, inks, printing inks, color filters and coating colors.
Illustrative examples of preferred binders for paint systems are
alkyd/melamine resin paints, acryl/melamine resin paints, cellulose
acetate/cellulose butyrate paints and two-pack system lacquers based on
acrylic resins which are crosslinkable with polyisocyanate.
According to observations made to date, the inventive fluorescent
maleimides I can be added in any desired amount to the material to be
colored, depending on the end use requirements. In the case of high
molecular weight organic materials, for example, the fluorescent
maleimides I prepared according to this invention can be used in an amount
in the range from 0.01 to 40, preferably from 0.01 to 5% by weight, based
on the total weight of the colored high molecular weight organic material.
For the preparation of paints systems, coating materials, color filters,
inks and printing inks, the corresponding high molecular weight organic
materials, such as binders, synthetic resin dispersions etc. and the
inventive fluorescent maleimides I are usually dispersed or dissolved
together, if desired together with customary additives such as
dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or
additional pigments or pigment precursors, in a common solvent or mixture
of solvents. This can be achieved by dispersing or dissolving the
individual components by themselves, or also several components together,
and only then bringing all components together, or by adding everything
together at once.
Hence, a further embodiment of the present invention relates to a method of
using the inventive fluorescent maleimides I for the preparation of
dispersions and the corresponding dispersions, and paint systems, coating
materials, color filters, inks and printing inks comprising the inventive
fluorescent maleimides I.
A particular embodiment of this invention concerns ink jet inks comprising
the inventive fluorescent compositions.
The desired ink may contain up to 30% by weight of the fluorescent
composition, but will generally be in the range of 0.1 to 10, preferably
from 0.1 to 8% by weight of the total ink composition for most thermal ink
jet printing applications.
Further, the inks usually contain polymeric dispersants such as random,
block, branched or graft polymers or copolymers. Most preferred are
polymeric dispersants made by the group transfer polymerization process,
because in general these are free from higher molecular weight species
that tend to plug pen nozzles.
Representative compounds useful for this purpose include e.g. polymers of
polyvinyl alcohol, cellulosics and ethylene oxide modified polymers, and
dispersant compounds containing ionisable groups such as acrylic acid,
maleic acid or sulfonic acid.
The polymeric dispersant is generally present in an amount in the range of
from 0.1 to 30, preferably from 0,1 to 8% by weight of the total ink
composition.
In addition to, or in place of the preferred polymeric dispersants,
surfactants may be used as dispersants. These may be anionic, nonionic, or
amphoteric surfactants. A detailed list of non-polymeric as well as some
polymeric dispersants is disclosed in the section on dispersants of
Manufacturing Confection Publishing Co., (1990) p. 110-129, McCutcheon's
Functional Materials, North America Edition.
Usually the ink contains an aqueous medium such as water or a mixture of
water and at least one water-soluble organic solvent. Water-soluble
organic solvents are well known, representative examples of which are
disclosed in e.g. U.S. Pat. No. 5,085,698. Selection of a suitable mixture
of water and water-soluble organic solvent depends on usually requirements
of the specific application such as desired surface tension and viscosity,
drying time of the ink, and the media substrate onto which the ink will be
printed.
Particularly preferred is a mixture of a water-soluble solvent having at
least two hydroxyl groups, e.g. diethylene glycol, and water, especially
deionized water.
In the event that a mixture of water and a water-soluble organic solvent is
used as aqueous medium, water usually would comprise from 30 to 95,
preferably 60 to 95% by weight, based on the total weight of the aqueous
medium.
The amount of aqueous medium generally is in the range of from 70 to 99.8,
preferably from 84 to 99.8%, based on the total weight of the ink.
The ink may contain other ingredients well known to those skilled in the
art such as surfactants to alter surface tension as well as to maximize
penetration. However, because surfactants may destabilize dispersions,
care should be taken to insure compatibility of the surfactant with the
other ink components. In general, in aqueous inks, the surfactants may be
present in amounts ranging from 0.01 to 5, preferably from 0.2 to 3% by
weight, based on the total weight of the ink.
Biocides may be used in the ink compositions to inhibit growth of
microorganisms. Sequestering agents such as EDTA may also be included to
eliminate deleterious effects of heavy metal impurities. Other known
additives, such as viscosity modifiers may also be added.
A further embodiment concerns the use of the inventive fluorescent
compounds I in phase change ink jet inks. The preparation of such inks is
well known in the art, e.g. described in detail in EP-A 816, 410.
For the pigmentation of high molecular weight organic material, the
inventive maleimides I, optionally in the form of masterbatches, usually
are mixed with the high molecular weight organic materials using roll
mills, mixing apparatus or grinding apparatus. Generally, the pigmented
material is subsequently brought into the desired final form by
conventional processes, such as calandering, compression molding,
extrusion, spreading, casting or injection molding. In order to prepare
non-rigid moldings or to reduce their brittleness it is often desired to
incorporate so-called plasticizers into the high molecular weight organic
materials prior to forming. Examples of compounds which can be used as
such plasticizers are esters of phosphoric acid, phthalic acid or sebacic
acid. The plasticizers can be added before or after the incorporation of
the inventive maleimides I into the polymers. It is also possible, in
order to achieve different hues, to add fillers or other coloring
constituents such as white, color or black pigments in desired amounts to
the high molecular weight organic materials in addition to the inventive
maleimides I.
For pigmenting lacquers, coating materials and printing inks the high
molecular weight organic materials and the inventive maleimides I, alone
or together with additives, such as fillers, other pigments, siccatives or
plasticizers, are generally dissolved or dispersed in a common organic
solvent or solvent mixture. In this case it is possible to adopt a
procedure whereby the individual components are dispersed or dissolved
individually or else two or more are dispersed or dissolved together and
only then are all of the components combined.
The present invention additionally relates to inks comprising a
coloristically effective amount of the pigment dispersion of the inventive
maleimides I.
Processes for producing inks especially for ink jet printing are generally
known and are described for example in U.S. Pat. No. 5,106,412.
The inks can be prepared, for example, by mixing the pigment dispersions
comprising the inventive maleimides I with polymeric dispersants.
The mixing of the pigment dispersions with the polymeric dispersant takes
place preferably in accordance with generally known methods of mixing,
such as stirring or mechanical mixing; it is preferably advisable to use
intensive mechanical mixers such as the so-called ULTRATURAX.RTM. from
Kunkel & Jahn, Staufen (Germany).
When mixing a maleimide I with polymeric dispersants it is preferred to use
a water-dilutable organic solvent.
The weight ratio of the pigment dispersion to the ink in general is chosen
in the range of from 0.001 to 75% by weight, preferably from 0.01 to 50%
by weight, based on the overall weight of the ink.
Examples of suitable polymeric dispersants are carboxyl-containing
polyacrylic resins such as polymeric methacrylic or crotonic acids,
especially those obtained by addition polymerization of acrylic acid or
acrylic acid and other acrylic monomers such as acrylates. Depending on
the field of use or when using maleimides I, it is also possible, if
desired, to admix a small proportion of a water-miscible organic solvent
in from 0.01 to 30% by weight, based on the overall weight of the ink,
and/or to admix water and/or bases so as to give a pH in the range from 7
to 11. It may likewise be advantageous to add preservatives, antifoams,
surfactants, light stabilizers and pH regulators, for example, to the ink
of the invention, depending on the field of use.
Examples of suitable pH regulators are inorganic salts such as lithium
hydroxide or lithium carbonate, quaternary ammonium hydroxide or ammonium
carbonate. Examples of preservatives and antifoams are, for example,
sodium dehydroacetate, 2,2-dimethyl-6-acetoxydioxane or ammonium
thioglycolate. It is also possible to employ known agents which regulate
the viscosity or the surface tension and are described in e.g. U.S. Pat.
No. 5,085,698.
Examples of water-miscible organic solvents are aliphatic C.sub.1 -C.sub.4
alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol,
tert.-butanol, ketones such as acetone methyl ethyl ketone, methyl
isobutyl ketone or diacetone alcohol, and also polyols, Cellosolves.RTM.
and carbitols, such as ethylene glycol, diethylene glycol, triethylene
glycol, glycerol, propylene gylcol, ethylene glycol monomethyl or
monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl
ether, tripropylene glycol methyl ether, ethylene glycol phenyl ether,
propylene glycol phenyl ether, diethylene glycol monomethyl or monoethyl
ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl or
monoethyl ether, and also N-methyl-2-pyrrolidone, 2-pyrrolidone,
N,N'-dimethylformamide or N,N'-dimethylacetamide.
If desired, the ink prepared as described above can be worked up further.
The working up of the ink can be carried out by the customary methods for
working up dispersions, by separation techniques, such as sieving or
centrifuging the coarse particles from the resulting dispersion. It has
been found advantageous, too, to carry out centrifuging in two stages of
different intensity, e.g. centrifuging in a first step for from ten
minutes to one hour at from 2000 to 4000 rpm and then, in a second step,
for from 10 minutes to one hour at from 6000 to 10000 rpm.
Following centrifuging or sieving, the dispersion usually can be used
directly as an ink for ink jet printing, for example.
The present invention additionally relates to a process for producing color
filters comprising a transparent substrate and applied thereon a red, blue
and green layer in any desired sequence, by using a red compound I and
known blue and green compounds. The different colored layers preferably
exhibit patterns such that over at least 5% of their respective surface
they do not overlap and with very particular preference do not overlap at
all.
The preparation and use of color filters or color-pigmented high molecular
weight organic materials are well-known in the art and described e.g. in
Displays 14/2, 1151 (1993), EP-A 784085, or GB-A 2,310,072.
The color filters can be coated for example using inks, especially printing
inks, which can comprise pigment dispersions comprising the inventive
maleimides I or can be prepared for example by mixing a pigment dispersion
comprising a maleimides I with chemically, thermally or photolytically
structurable high molecular weight organic material (so-called resist).
The subsequent preparation can be carried out, for example, in analogy to
EP-A 654 711 by application to a substrate, such as a LCD, subsequent
photostructuring and development.
Particular preference for the production of color filters is given to
pigment dispersions comprising a maleimides I which possess non-aqueous
solvents or dispersion media for polymers.
The present invention relates, moreover, to toners comprising a pigment
dispersion containing a maleimide I or a high molecular weight organic
material pigmented with a maleimide I in a coloristically effective
amount. In a particular embodiment of the process of the invention,
toners, coating materials, inks or colored plastics are prepared by
processing masterbatches of toners, coating materials, inks or colored
plastics in roll mills, mixing apparatus or grinding apparatus.
The present invention additionally relates to colorants, colored plastics,
polymeric ink particles, or non-impact-printing material comprising an
inventive maleimide I pigment, preferably in the form of a dispersion, or
a high molecular weight organic material pigmented with a maleimide I in a
coloristically effective amount.
A coloristically effective amount of the pigment dispersion according to
this invention comprising an inventive maleimide I denotes in general from
0.0001 to 99.99% by weight, preferably from 0.001 to 50% by weight and,
with particular preference, from 0.01 to 50% by weight, based on the
overall weight of the material pigmented therewith.
Further, the inventive compounds I can be used for textile application and
for the dying of paper.
A further embodiment of the present invention relates to the use of the
fluorescent maleimides of the general formula I and of the formula Ia
##STR26##
for the preparation of and use in organic electroluminescent ("EL")
devices. Such EL devices are well-known in the art (e.g. described in
Appl. Phys. Lett. 51 (1987) 913).
In a preferred embodiment EL devices are used which have the following
compositions:
(i) an anode/a hole transporting layer/an electron transporting layer/a
cathode
in which the inventive compounds I or compounds Ia are used either as
positive-hole transport compounds, which is exploited to form the light
emitting and hole transporting layers, or as electron transport compounds,
which can be exploited to form the light-emitting and electron
transporting layers, and
(ii) an anode/a hole transporting layer/a light-emitting layer/an electron
transporting layer/a cathode,
in which the inventive compounds I or compounds Ia form the light-emitting
layer regardless of whether they exhibit positive-hole or electron
transport properties in this constitution. It is possible that the light
emitting layer can consist of two or more fluorescent substances of
formulae I or Ia for energy donor(s) and energy acceptor(s).
The devices can be prepared in several well-known ways. Generally, vacuum
evaporation is extensively used for the preparation. The devices can be
prepared in several ways. Usually, vacuum evaporation is extensively used
for the preparation. Preferably, the organic layers are laminated in the
above order on a commercially available indium-tin-oxide ("ITO") glass
substrate held at room temperature, which works as the anode in the
constitutions. The membrane thickness is preferably in the range of 1 to
10.sup.4 nm, more preferably 1 to 5000 nm, more preferably 1 to 10.sup.3
nm, more preferably 1 to 500 nm. The cathode metal such as Mg/Ag alloy and
Li--Al binary system of ca. 200 nm is laminated on the top of the organic
layers. The vacuum during the deposition is preferably less than 0.1333 Pa
(1.times.10.sup.-3 Torr), more preferably less than 1.333.times.10.sup.-3
Pa (1.times.10.sup.-5 Torr), more preferably less than
1.333.times.10.sup.-4 Pa (1.times.10.sup.-6 Torr).
As anode usual anode materials which possess high work function such as
metals like gold, silver, copper, aluminum, indium, iron, zinc, tin,
chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten
and the like, metallic alloys such as magnesium/copper, magnesium/silver,
magnesium/aluminum, aluminum/indium and the like, semiconductors such as
Si, Ge, GaAs and the like, metallic oxides such as indium-tin-oxide
("ITO"), ZnO and the like, metallic compounds such as Cul and the like,
and furthermore, electroconducting polymers such polyacetylene,
polyaniline, polythiophene, polypyrrole, polyparaphenylene and the like,
preferably ITO, most preferably ITO on glass as substrate can be used. Of
these electrode materials, metals, metallic alloys, metallic oxides and
metallic compounds can be transformed into electrodes, for example, by
means of the sputtering method. In the case of using a metal or a metallic
alloy as a material for an electrode, the electrode can be formed also by
the vacuum deposition method. In the case of using a metal or a metallic
alloy as a material forming an electrode, the electrode can be formed,
furthermore, by the chemical plating method (see for example, Handbook of
Electrochemistry, pp 383-387, Mazuren, 1985). In the case of using an
electroconducting polymer, an electrode can be made by forming it into a
film by means of anodic oxidation polymerization method onto a substrate
which is previously provided with an electroconducting coating. The
thickness of an electrode to be formed on a substrate is not limited to a
particular value, but, when the substrate is used as a light emitting
plane, the thickness of the electrode is preferably within the range of
from 1 nm to 100 nm, more preferably, within the range of from 5 to 50 nm
so as to ensure transparency.
In a preferred embodiment ITO is used on a substrate having an ITO film
thickness in the range of from 10 nm (100 .ANG.) to 1.mu. (10000 .ANG.),
preferably from 20 nm (200 521 ) to 500 nm (5000 .ANG.). Generally, the
sheet resistance of the ITO film is chosen in the range of not more than
100 .OMEGA./cm.sup.2, preferred from not more than 50 .OMEGA./cm.sup.2.
Such anodes are commercially available e.g. from e.g. Japanese
manufacturers such as Geomatech Co.Ltd., Sanyo Vacuum Co. Ltd., Nippon
Sheet Glass Co. Ltd.
As substrate either an electroconducting or electrically insulating
material can be used. In case of using an electroconducting substrate, a
light emitting layer or a positive hole transporting layer is directly
formed thereupon, while in case of using an electrically insulating
substrate, an electrode is firstly formed thereupon and then a light
emitting layer or a positive hole transporting layer is superposed.
The substrate may be either transparent, semi-transparent or opaque.
However, in case of using a substrate as an indicating plane, the
substrate must be transparent or semi-transparent.
Transparent electrically insulating substrates are, for example, inorganic
compounds such as glass, quartz and the like, organic polymeric compounds
such as polyethylene, polypropylene, polymethylmethacrylate,
polyacrylonitrile, polyester, polycarbonate, polyvinylchloride,
polyvinylalcohol, polyvinylacetate and the like. Each of these substrates
can be transformed into a transparent electroconducting substrate by
providing it with an electrode according to one of the methods described
above.
As examples of semi-transparent electrically insulating substrates, there
are inorganic compounds such as alumina, YSZ (yttrium stabilized zirconia)
and the like, organic polymeric compounds such as polyethylene,
polypropylene, polystyrene, epoxy resin and the like. Each of these
substrates can be transformed into a semi-transparent electroconducting
substrate by providing it with an electrode according to one of the
abovementioned methods.
As examples of opaque electroconducting substrates, there are metals such
as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper,
silver, gold, platinum and the like, various elctroplated metals, metallic
alloys such as bronze, stainless steel and the like, semiconductors such
as Si, Ge, GaAs, and the like, electroconducting polymers such as
polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene
and the like.
A substrate can be obtained by forming one of the above listed substrate
materials to a desired dimension. It is preferred that the substrate has a
smooth surface. Even if it has a rough surface, however, it will not cause
any problem for practical use, provided that it has round unevenness
having a curvature of not less than 20 .mu.m. As for the thickness of the
substrate, there is no restriction as far as it ensures sufficient
mechanical strength.
As cathode usual cathode materials which possess low work function such as
alkali metals, earth alkaline metals, group 13 elements, silver, and
copper as well as alloys or mixtures thereof such as sodium, lithium,
potassium, sodium-potassium alloy, magnesium, magnesium-silver alloy,
magnesium-copper alloy, magnesium-aluminum alloy, magnesium-indium alloy,
aluminum, aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium,
calcium, and materials exemplified in EP-A 499,011 such as
electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline,
polyacetylene etc., preferably Mg/Ag alloys, or Li--Al compositions can be
used.
In a preferred embodiment magnesium-silver alloy or a mixture of magnesium
and silver mixture, or lithium-aluminum alloy or a mixture of lithium and
aluminum can be used in a film thickness in the range of from 10 nm (100
.ANG.) to 1 .mu.m (10000 .ANG.), preferably from 20 nm (200 .ANG.) to 500
nm (5000 .ANG.).
Such cathodes can be deposited on the foregoing electron transporting layer
by known vacuum deposition techniques described above.
In a preferred ambodiment of this invention a light-emitting layer can be
used between the hole transporting layer and the electron transporting
layer. Usually it is prepared by forming a thin film of a maleimide of
formula I on the hole transporting layer.
As methods for forming said thin film, there are, for example, the vacuum
deposition method, the spin-coating method, the casting method, the
Langmuir-Blodgett ("LB") method and the like. Among these methods, the
vacuum deposition method, the spin-coating method and the casting method
are particularly preferred in view of ease in operation and cost. In case
of forming a thin film using a fluorescent maleimide I by means of the
vacuum deposition method, the conditions under which the vacuum deposition
is carried out are usually strongly dependent on the properties, shape and
crystalline state of the compound. However, optimum conditions can be
selected for example within the range of from 100 to 400.degree. C. in
temperature for the heating boat, -100 to 350.degree. C. in substrate
temperature, 1.33.times.10.sup.4 Pa (1.times.10.sup.2 Torr) to
1.33.times.10.sup.-4 Pa (1.times.10.sup.-6 Torr) in pressure and 1 pm to 6
nm/sec in deposition rate.
In an organic EL element, the thickness of the light emitting layer thereof
is one of the factors determining its light emission properties. For
example, if a light emitting layer is not sufficiently thick, a short
circuit can occur quite easily between two electrodes sandwiching said
light emitting layer, and therefor, no EL emission is obtained. On the
other hand, if the light emitting layer is excessively thick, a large
potential drop occurs inside the light emitting layer because of its high
electrical resistance, so that the threshold voltage for EL emission
increases. Accordingly, it is necessary to limit the thickness of an
organic light emitting layer within the range of from 5 nm to 5 .mu.m. A
preferable thickness is within the range of from 10 nm to 500 nm.
In the case of forming a light emitting layer by using the spin-coating
method and the casting method, the coating can be carried out using a
solution prepared by dissolving the fluorescent maleimide I in a
concentration of from 0.0001 to 90% by weight in an appropriate organic
solvent such as benzene, toluene, xylene, tetrahydrofurane,
methyltetrahydrofurane, N,N-dimethylformamide, dichloromethane,
dimethylsulfoxide and the like. Herein, the higher the concentration of
fluorescent maleimide I, the thicker the resulting film, while the lower
the concentration, the thinner the resulting film. However, if the
concentration exceeds 90% by weight, the solution usually is so viscous
that it no longer permits forming a smooth and homogenous film. On the
other hand, as a rule, if the concentration is less than 0.0001% by
weight, the efficiency of forming a film is too low to be economical.
Accordingly, a preferred concentration of the fluorescent maleimide I is
within the range of from 0.01 to 80% by weight. In the case of using the
above spin-coating or casting method, it is possible to further improve
the homogeneity and mechanical strength of the resulting layer by adding a
polymer binder in the solution for forming the light emitting layer. In
principle, any polymer binder may be used, provided that it is soluble in
a solvent in which the fluorescent maleimide I is dissolved. Examples of
such polymer binders are polycarbonate, polyvinylalcohol,
polymethacrylate, polymethylmethacrylate, polyester, polyvinylacetate,
epoxy resin and the like. A solution for forming a light emitting layer
may have any concentrations of the fluorescent maleimide I, of a polymer
binder and solvent. However, if the solid content composed of the polymer
binder and fluorescent maleimide I exceeds 99% by weight, the fluidity of
the solution is usually so low that it is impossible to form a light
emitting layer excellent in homogeneity. On the other hand, if the content
of fluorescent maleimide I is substantially smaller than that of the
polymer binder, in general the electrical resistance of said layer is very
large, so that it does not emit light unless a high voltage is applied
thereto. Furthermore, since the concentration of fluorescent maleimide I
in the layer is small in this case, its light emission efficiency is
relatively low. Accordingly, the preferred composition ratio of a polymer
binder to fluorescent maleimide I is chosen within the range of from 10:1
to 1:50 by weight, and the solid content composed of both components in
the solution is preferably within the range of from 0.01 to 80% by weight,
and more preferably, within the range of about 0.1 to 60% by weight.
In the case of forming a light emitting layer by the spin-coating method or
casting method, the thickness of said layer may be selected in the same
manner as in the case of forming a light emitting layer by the vacuum
deposition method. That is, the thickness of the layer preferably is
chosen within the range of from 5 nm to 5 .mu.m, and more preferably,
within the range of from 10 nm to 500 nm.
As hole-transporting layers known organic hole transporting compounds such
as polyvinyl carbazole,
##STR27##
a triphenylamine derivative ("TPD") compound disclosed in J.Amer.Chem.Soc.
90 (1968) 3925
##STR28##
wherein Q.sub.1 and Q.sub.2 each represent a hydrogen atom or a methyl
group;
a compound disclosed in J. Appl. Phys. 65(9) (1989) 3610
##STR29##
a stilbene based compound
##STR30##
wherein T and T.sub.1 stand for an organic rest
a hydrazone based compound
##STR31##
and the like.
Compounds to be used as a positive hole transporting material are not
restricted to the above listed compounds. Any compound having a property
of transporting positive holes can be used as a positive hole transporting
material such as triazole derivatives, oxadiazole derivatives, imidazole
derivatives, polyarylalkane derivatives, pyrazoline derivative, pyrazolone
derivatives, phenylene diamine derivatives, arylamine derivatives, amino
substituted chalcone derivatives, oxazole derivatives, stilbenylanthracene
derivatives, fluorenone derivatives, hydrazone derivatives, stilbene
derivatives, copolymers of aniline derivatives, electro-conductive
oligomers, particularly thiophene oligomers, porphyrin compounds, aromatic
tertiary amine compounds, stilbenyl amine compounds etc. Particularly,
aromatic tertiary amine compounds such as
N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl,
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diaminobiphenyl (TPD),
2,2'-bis(di-p-torylaminophenyl)propane,
1,1'-bis(4-di-torylaminophenyl)-4-phenylcyclohexane,
bis(4-dimethylamino-2-methylphenyl)phenylmethane,
bis(4-di-p-tolylaminophenyl)phenylmethane,
N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl,
N,N,N',N'-tetraphenyl-4,4'-diaminodiphenylether,
4,4'-bis(diphenylamino)quaterphenyl, N,N,N-tri(p-tolyl)amine,
4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)stilyl]stilbene,
4-N,N-diphenylamino-(2-diphenylvinyl)benzene,
3-methoxy-4'-N,N-diphenylaminostilbene, N-phenylcarbazole etc.
Furthermore, 4,4'-bis[N-(1-naphtyl)-N-phenylamino]biphenyl disclosed in
U.S. Pat. No. 5,061,569, the compounds in which three triphenylamine units
are bound to a nitrogen atom like "star-burst" structure e.g.
4,4',4"-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine disclosed in
EP-A 508,562.
A positive hole transporting layer can be formed by preparing an organic
film containing at least one positive hole transporting material on the
anode. The positive hole transporting layer can be formed by the vacuum
deposition method, the spin-coating method, the casting method, the LB
method and the like. Of these methods, the vacuum deposition method, the
spin-coating method and the casting method are particularly preferred in
view of ease and cost.
In the case of using the vacuum deposition method, the conditions for
deposition may be chosen in the same manner as described for the formation
of a light emitting layer (see above). If it is desired to form a positive
hole transporting layer comprising more than one positive hole
transporting material, the coevaporation method can be employed using the
desired compounds.
In the case of forming a positive hole transporting layer by the
spin-coating method or the casting method, the layer can be formed under
the conditions described for the formation of the light emitting layer
(see above).
As in the case of forming a light emitting layer using a solution
containing a polymer binder, a smoother and more homogeneous positive hole
transporting layer can be formed by using a solution containing a binder
and at least one positive hole transporting material. The coating using
such a solution can be performed in the same manner as in cases of forming
a light emitting layer using a polymer binder. Any polymer binder may be
used, provided that it is soluble in a solvent in which at least one
positive hole transporting material is dissolved. Examples of appropriate
polymer binders and of appropriate and preferred concentrations are given
above when describing the formation of a light emitting layer.
The thickness of a positive hole transporting layer is preferably chosen in
the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more
preferably from 2 to 50 nm.
As electron transporting materials for an electron-transporting layer it is
preferred to have a high electron injection efficiency from the cathode
and a high electron mobility. The following materials can be exemplified
for electron transporting materials:
tris(8-hydroxyquinolinoato)aluminum(III) and its derivatives,
bis(10-hydroxybenzo[h]quinolinolato)beryllium(II) and its derivatives,
oxadiazole derivatives such as
2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1,3,4-oxadiazole and its dimer
systems such as 1,3-bis(4-tert.-butylphenyl-1,3,4)oxadiazolyl)-biphenylene
and 1,3-bis(4-tert.-butylphenyl-1,3,4-oxadiazolyl)phenylene, triazole
derivatives, phenanthroline derivatives or perylene tetracarboxylic acid
derivatives such as disclosed in Appl. Phys. Lett. 48 (2) (1986) 183.
An electron transporting layer can be formed by preparing an organic film
containing at least one electron transporting material on the hole
transporting layer or on the light-emitting layer. The electron
transporting layer can be formed by the vacuum deposition method, the
spin-coating method, the casting method, the LB method and the like.
As in the case of forming a light emitting layer or a positive hole
transporting layer by using a solution containing a polymer binder, a
smoother and more homogeneous electron transporting layer can be formed by
using a solution containing a binder and at least one electron
transporting material.
The thickness of an electron transporting layer is preferably chosen in the
range of from 0.5 nm to 1000 nm, preferably from 1 nm to 100 nm, more
preferably from 2 to 50 nm.
Another embodiment relates to the use of the inventive compounds I and
known compounds la as UV fluorescent materials for void detection.
Especially preferred is the use for so-called OEM (original equipment
manufacturer) applications such as automotive electrocoats and subsequent
layers, for example primer surfacers, as well as industrial applications
in general.
The present invention therefore relates to coating compositions comprising
(a) an organic film-forming binder and (b) at least one compound of the
formula I or Ia.
The coating composition is optionally solvent based, water based or solvent
free.
Examples of coating materials are lacquers, paints, varnishes, powder
coatings or electrocoats. These usually contain an organic film-forming
binder in addition to other, optional components.
Preferred organic film-forming binders are epoxy resins, polyurethane
resins, amino resins, acrylic resins, acrylic copolymer resins, polyvinyl
resins, phenolic resins, urea resins, melamine resins, styrene/butadiene
copolymer resins, vinyl/acrylic copolymer resins, polyester resins or
alkyd resins, or a mixture of two or more of these resins, or an aqueous
basic or acidic dispersion of these resins or mixtures of these resins, or
an aqueous emulsion of these resins or mixtures of these resins, or hybrid
systems based on, for example, epoxy acrylates.
More specifically, the alkyd resins can be water-dilutable alkyd resin
systems which can be employed in air-drying form or in the form of stoving
systems, optionally in combination with water-dilutable melamine resins;
the systems may also be oxidatively drying, air-drying or stoving systems
which are optionally employed in combination with aqueous dispersions
based on acrylic resins or copolymers thereof, with vinyl acetates, etc.
The acrylic resins can be pure acrylic resins, epoxy acrylate hybrid
systems, acrylic acid or acrylic ester copolymers, combinations with vinyl
resins, or copolymers with vinyl monomers such as vinyl acetate, styrene
or butadiene. These systems can be air-drying systems or stoving systems.
In combination with appropriate polyamine crosslinkers, water-dilutable
epoxy resins exhibit excellent mechanical and chemical resistance. If
liquid epoxy resins are used, the addition of organic solvents to aqueous
systems can be omitted. The use of solid resins or solid-resin dispersions
usually necessitates the addition of small amounts of solvent in order to
improve film formation.
Preferred epoxy resins are those based on aromatic polyols, especially
those based on bis-phenols. The epoxy resins are employed in combination
with crosslinkers. The latter may in particular be amino- or
hydroxy-functional compounds, an acid, an acid anhydride or a Lewis acid
or a blocked isocyanate. Examples thereof are polyamines, polyaminoamides,
polysulfide-based polymers, polyphenols, boron fluorides and their complex
compounds, polycarboxylic acids, 1,2-dicarboxylic anhydrides, pyromellitic
dianhydride, ot toluoyl di-iso-cyanates.
Polyurethane resins are derived from polyethers, polyesters and
polybutadienes with terminal hydroxyl groups, on the one hand, and from
aliphatic or aromatic polyisocyanates on the other hand.
Examples of suitable polyvinyl resins are polyvinylbutyral, polyvinyl
acetate or copolymers thereof.
Suitable phenolic resins are synthetic resins in the course of whose
construction phenols are the principal component, i.e. in particular
phenol-, cresol-, xylenol- and resorcinol-form-aldehyde resins,
alkylphenolic resins, and condensation products of phenols with
acetaldehyde, furfurol, acrolein or other aldehydes. Modified phenolic
resins are also of interest.
The coating compositions may additionally comprise one or more components
taken, for example, from the group consisting of pigments, dyes, fillers,
flow control agents, dispersants, thixotropic agents, adhesion promoters,
antioxidants, light stabilizers and curing catalysts.
The pigments are, for example, titanium dioxide, iron oxide, aluminium
bronze or phthalo-cyanine blue.
Examples of fillers are talc, alumina, aluminium silicate, barytes, mica,
and silica.
Flow control agents and thixotropic agents are based, for example, on
modified bentonites.
Adhesion promoters are based, for example, on modified silanes.
The claimed fluorescent compounds can be added to the coating material
during its preparation, for example during pigment dispersion by grinding,
or they are dissolved in a solvent and the solution is then stirred into
the coating composition.
In the preparation of the organic film-forming binder by addition
polymerization or condensation polymerization of monomers, the claimed
fluorescent compounds can be mixed in in solid form, or dissolved, with
the monomers even prior to the polymerization reaction.
The inventive maleimides I and other compounds of the formula la as well as
compounds belonging to the group of dyestuffs exhibiting edge fluorescence
are used in amounts of preferably 0.01% to 5% by weight, more preferably
from 0.5 to 1.0% by weight, based on the total solids of the formulation
containing no fluorescent agent.
The coating materials can be applied to the substrate by the customary
techniques, for example by spraying, dipping, spreading or
electrodeposition. In many cases, a plurality of coats are applied. The
claimed maleimides I or the known compounds la as well as compounds
belonging to the group of dyestuffs exhibiting edge fluorescence usually
are added primarily to the base layer (primer), however, they can also be
added to the intermediate coat, for example a primer surfacer, or topcoat,
as well. Depending on whether the binder is a physically, chemically or
oxidatively drying resin or a heat-curing or radiation-curing resin, the
coating is cured at room temperature or by heating (stoving) or by
irradiation.
Once the coating compositions are cured, the corresponding coatings can be
inspected with the use of a UV-lamp. Defects or voids as a result of
misapplication or artificially applied defects can be easily detected,
because the used fluorescent compounds exhibit intense fluorescence only
at the voids (so-called "edge fluorescence").
Hence, another preferred embodiment of this invention relates to a
composition comprising a dyestuff exhibiting edge fluorescence.
A further preferred embodiment of this invention relates to a method of
inspecting the surface of a body comprising the steps of:
(a) covering a surface with a composition comprising a compound exhibiting
edge fluorescence,
(b) inspecting the thus covered surface with ultraviolet light for visible
light, such being indicative of faults in the surface.
Preferably, inspection is done using a high intensity black light (UV-A,
320-400 nm), preferably under low light conditions. A suitable lamp is
available from Spectronics Corporation Inc. (Westbury, N.Y.).
Preferably, the edge fluorescence exhibiting compound is a maleimide of
formulae I or la are used, most preferably
1,1-(1,2-ethanediyl)bis[3,4-diphenyl]-1H-pyrrole-2,5-dione
##STR32##
A further preferred embodiment relates to an article of manufacture
comprising: a body having a surface to be covered; a layer of coating
material on the surface of the body, fluorescing means blended with said
coating material for emitting identifiable visible light in response to
exposure to ultraviolet light.
Preferably, the fluorescing means is a compound of formula I or la,
particularly preferred is
1,1'-(1,2-ethanediyl)bis[3,4-diphenyl]-1H-pyrrole-2,5-dione.
The claimed fluorescent compounds as well as the compositions allow easy
quality assurance, instant possibility of repair, easy longer-term
inspection. Further, compared to optical brighteners, a superior
solubility is observed which makes an incorporation more easy. In
addition, the claimed materials show fluorescence in the solid state,
whereas optical brighteners must be soluble in the resin or polymer to
exhibit fluorescence. The claimed compounds and compositions also show a
superior photostability and none to less yellowing compared to optical
brighteners upon UV-exposure, i.e. optical brighteners photochemically
decompose under UV-light within less than 24 to 100 hours with formation
of colored products leading to discoloration of e.g. white coatings. Also
the claimed compounds and compositions migrate less than and contaminate
the working environment less than optical brighteners. A big advantage is
the exhibition of the so-called edge fluorescence meaning that
fluorescence is observed only at voids and not at the whole surface which
gives much better contrast compared to e.g. optical brighteners and allows
also the detection of minor defects or damages. Too, the inventive
compounds and composition have no or only minimal impact on the paint
color in comparison to dyes, i.e. they can be even used in white pigmented
systems. Further, the inventive materials are useful in dark and white
pigmented systems where optical brighteners fail, i.e. in dark pigmented
systems fluorescence and subsequently voids are difficult to detect in
known systems, in white pigmented systems fluorescence is too intense
(whole surface) which in turn makes it very difficult to identify voids in
systems of the prior art. Finally, the found superior photostability of
the inventive materials compared to optical brighteners allows long-term
void detection, i.e. inspection after months or years after the
application. Particularly,
1,1'-(1,2-ethanediyl)bis[3,4-diphenyl]-1H-pyrrole-2,5-dione is suitable
for detecting defects such as craters (voids) and poor coverage: an unique
edge fluorescence phenomenon is shown when a cured coating is scratched.
The technique also works over uneven surfaces, e.g. weld seams.
EXAMPLES
(A) Preparation of Diarylmaleic Anhydrides
Example 1
(a) To 301 g (2.26 mol) of AlCl.sub.3 in CH.sub.2 Cl.sub.2 (750 ml) a
mixture of 383 g (2.25 mol) of 4-phenoxybenzene and 205 g (1.50 mol) of
ethyl chloroglyoxylate in CH.sub.2 Cl.sub.2 (750 ml) is added dropwise at
ice-bath temperature during one hour. Thereafter, the mixture is gradually
warmed up to room temperature and stirred overnight. Then, the reaction
mixture is poured onto ice. The aq. solution is acidified to pH 3 with
aqueous HCl solution, followed by an extraction with CH.sub.2 Cl.sub.2.
The extract is dried over anhydrous MgSO.sub.4. The desired product is
purified by silica gel column chromatography using CH.sub.2 Cl.sub.2
-hexane mixture as eluent. 338 g of colorless oily 4-phenoxyphenyl
glyoxylic acid ethyl ester is obtained (83%).
(b) 338 g (1.25 mol) of the above obtained product is treated with 60.4 g
(1.45 mol) of NaOH (96%) in 1 l of water and 1 of EtOH under reflux for 2
h. The mixture is then acidified to pH 3, and then 4-phenoxyphenyl
glyoxylic acid is extracted with CH.sub.2 Cl.sub.2. 310 g of oil is
obtained as a crude product. This product is used for next the below
reaction without further purification.
(c) To 167 g of 4-phenoxyphenyl glyoxylic acid 160 ml (3.30 mol) of
hydrazine monohydrate are carefully added through a condenser under reflux
over 45 min. After cooling the reaction mixture to 100.degree. C., 176 g
(2.68 mol) of KOH (85% in water) are carefully added over 45 min., and
then the reaction mixture is heated to reflux for 45 min. Excess hydrazine
is removed by distillation, and the mixture is acidified with diluted
aqueous HCl to pH 3, followed by an extraction with CH.sub.2 Cl.sub.2. The
desired 4-phenoxyphenyl acetic acid is purified by repeated
crystallization from hot hexane. 122 g of white solid are obtained (80%).
(d) 142 g (582 mmol) of 4-phenoxyphenyl glyoxylic acid are treated with
68.6 g (612 mmol) of tert.-BuOK in MeOH to obtain the corresponding
potassium salt. The obtained white solid is then filtered, followed by
washing with MeOH. 162 g of white solid are obtained. 150 g (535 mmol) of
this white solid are mixed with 120 g (525 mmol) of 4-phenoxyphenyl acetic
acid in 1 l of acetic anhydride and heated to reflux for two hours. After
removal of acetic anhydride by evaporation in an atmosphere under reduced
pressure, the obtained yellow solid is washed with acetone and ethyl
acetate affording 217 g of yellow solid 3,4-di(4-phenoxyphenyl) maleic
anhydride (93%).
Examples 2a-13a
Example 1a is repeated with the differences mentioned in the below Table 1:
TABLE 1
AlCl.sub.3 in CH.sub.2 Cl.sub.2 amount ethyl
chloro- in CH.sub.2 Cl.sub.2 treatment in ice-bath stirring after warming
yield
ex. [g] [ml] R.sub.18 -H [g] glyoxylate [g] [ml]
[h] to r.t. [h] [%]
2a 68.4 300 3-dibenzofurane 51.2 45.0 400
1 2 89
3a 67.3 200 4-methoxybenzene 43.4 60.1 200
1 1 82
4a 15.0 100 4-phenylthiobenzene 18.6 14.3 150
1/2 2/3 76
5a 14.9 300 3,4-dimethoxybenzene 13.8 14.3 150
1/2 2/3 33
6a.sup.1) 23.0 60 4-dimethylaminobenzene 12.2 15.0
60 1/6 12 44
7a.sup.2) 45.0 200 4-diphenylaminobenzene 76.5 42.6
200 2/3 21/2 47
8a 20.5 150 3-(N-ethyl)-carbazole 19.5 14.4 150
1/4 2 72
9a 23.44 60 1-naphthaline 12.8 15.0 60
11/2 12 92
10a 37.3 100 4-methoxy-1-naphthaline 25.5 23.9
100 5/12 7/12 95
11a 22.1 100 4-morpholinobenzene 24.5 21.5 100
3 12 43
12a 27.4 60 1-pyrene 24.3 18.1 60
5/12 12 83
13a 13.6 35 9-anthrene 10.8 9.10 65
1/6 12 84
Example 14a
To 8.56 g (60.2 mmol) of 3,4-ethylenedioxy-2-thiophene in tetrahydrofurane
("THF") (50 ml) 40 ml of 1.6 M n-BuLi hexane solution (64 mmol) are added
dropwise at -100.degree. C. over 10 min. The obtained solution is added to
17.6 g (121 mmol) of diethyl oxalate in THF (50 ml) at -100.degree. C.
through a canula during two hours. After completion of the addition, the
obtained mixture is gradually warmed up to room temperature and stirred
for four hours. Then, an aqueous NH.sub.4 Cl solution is added to this
reaction mixture. After removal of THF and hexane, the product is
extracted with CH.sub.2 Cl.sub.2. The extract is dried over anhydrous
MgSO.sub.4. Then, the desired product is purified by silica gel column
chromatography using CH.sub.2 Cl.sub.2 -hexane mixture as eluent. 12.2 g
of yellow solid 3,4-ethylenedioxy-2-thienyl glyoxylic acid ethyl ester are
obtained (84%).
Example 15a
To 10.1 9 (48.8 mmol) of naphthalene in 200 ml THF 65 ml of 1.6 M n-BuLi
hexane solution (104 mmol) are added dropwise at -100.degree. C. during 20
min. The obtained solution is added to 30 ml (221 mmol) of diethyl oxalate
during 5 min. After completion of the addition, the obtained mixture is
gradually warmed up to room temperature and stirred for 17.5 hours. Then,
water is added to this reaction mixture. After removal of THF and hexane,
the product is extracted with CH.sub.2 Cl.sub.2. The extract is dried over
anhydrous MgSO.sub.4. Then, the desired product is purified by silica gel
column chromatography using CH.sub.2 Cl.sub.2 -hexane mixture as eluent.
3.76 9 of yellow oil 2-naphthyl glyoxylic acid ethyl ester as a mixture
together with diethyl oxalate. A .sup.1 H-NMR-spectrum of the mixture
indicated the presence of the desired product with 56.4% in the mixture
(19. 1% yield). The mixture is used for the next reaction step (example
15b) without any further purification.
Examples 2b to 16b
example 1 b is repeated, however, the reaction parameters of Table 2 are
used (ex. 16b, 4-acetylaminophenyl glyoxylic acid ethyl ester, is prepared
according to the method described in J. Org. Chem., 1981, 46, 134)
TABLE 2
ester VIII R.sub.18 amount NaOH water EtOH duration of reflux
yield
ex. (R.sub.20 = ethyl) [g] [g] [ml] [ml] [h]
workup [%]
2b 3-dibenzofuryanyl 71.6 12.4 200 200 3
A 83
3b 4-methoxyphenyl 53.0 12.2 250 250 1
B 93
4b 4-phenylthiophenyl 20.6 3.29 70 70 4
C 63
5b 3,4-dimethoxyphenyl 7.58 1.51 30 30 1
D 90
6b 4-dimethylaminophenyl 9.58 2.63 50 50 5
E 56
7b 4-diphenylaminophenyl 50.6 6.76 150 150 2
D 95
8b 3-(N-ethyl)-carbazole 20.9 3.29 70 70 3
D 100
9b 1-naphthyl 20.9 5.85 100 100 31/2
D 95
10b 4-methoxy-1-naphthyl 39.3 6.98 150 150 2
F 91
11b 4-morpholinophenyl 16.7 2.96 60 60 11/2
G 93
12b 1-pyrenyl 29.7 4.51 100 100 4
H 62
13b 9-anthryl 13.6 2.29 60 60 1
I 99
14b 3,4-ethylenedioxy-2-thienyl 12.0 2.17 50 50 4
J 89
15b 2-naphthyl 3.76 1.49 40 40 2
K 90
Workup
A: The mixture is acidified to pH 3, and then the product is collected by
filtration and subsequent washing with water and then CH.sub.2 Cl.sub.2.
B: The mixture is acidified to pH 3, and then the product is collected by
filtration and subsequent washing with water.
C: The mixture is acidified to pH 3, and then the product is extracted with
CH.sub.2 Cl.sub.2. The extract is dried over anhydrous MgSO.sub.4. The
desired product is purified by silica gel column chromatography using
CH.sub.2 Cl.sub.2 -MeOH mixture as eluent. 11.6 g of a brown oil are
obtained.
D: The mixture is acidified to pH 3, and then the product is extracted with
CH.sub.2 Cl.sub.2. After removal of CH.sub.2 Cl.sub.2, washing with hexane
affords 11.6 g of a white solid.
E: After acidifying the mixture, the resulting solid is filtered off,
followed by washing with water and acetone. The desired product is
purified by silica gel column chromatography using CH.sub.2 Cl.sub.2 -MeOH
mixture as eluent. 4.65 g of a yellow solid are obtained.
F: The mixture is acidified, and then the product is extracted with
CH.sub.2 Cl.sub.2. The extract is dried over anhydrous MgSO.sub.4. After
removal of the solvent, 32.0 g of a pale yellow solid are obtained.
G: The mixture is acidified to pH 3, and then the resulting white solid is
filtered, followed by washing with water and acetone. 15.1 g of a white
solid are obtained as a crude product. This product is used for the next
reaction step without further purification.
H: The mixture is acidified to pH 3, and then the resulting white solid is
filtered, followed by washing with water, acetone, and CH.sub.2 Cl.sub.2.
16.8 g of a yellow solid are obtained as a crude product. This product is
used for the next reaction step without further purification.
I: The mixture is acidified, and then the product is extracted with
CH.sub.2 Cl.sub.2. The extract is dried over anhydrous MgSO.sub.4. After
removal of the solvent, 12.1 g of an orange solid are obtained.
J: The mixture is acidified, and then the resulting solid is filtered,
followed by washing with water and a small portion of CH.sub.2 Cl.sub.2.
9.47 g of a yellow solid are obtained.
K: The mixture is acidified, and then the product is extracted with
CH.sub.2 Cl.sub.2. The desired acid is purified by silica gel column
chromatography using CH.sub.2 Cl.sub.2 -MeOH mixture as eluent. 1.94 g of
a yellow solid are obtained.
Examples 2c to 15c, and 19c:
example 1 c is repeated, however, the educts and reaction parameters of
Table 3 are used (2-(4- methoxyphenyl)-acetic acid (corresponding to ex.
3c), 2-(3,4-dimethoxyphenyl)-acetic acid (corresponding to ex. 5c), 2-(4-
diphenylaminophenyl)-acetic acid (corresponding to ex. 6c),
2-(1-naphthyl)-acetic acid (corresponding to ex. 9c),
2-(2-naphthyl)-acetic acid (corresponding to ex. 15c) and
chloropheylacetic acid (corresponding to ex. 19c) are commercially
available):
TABLE 3
acid VI amount H.sub.2 NNH.sub.2.H.sub.2 O duration
of reflux KOH duration of relux yield
ex. R.sub.18 [g] [ml] [min] [g]
[h] workup [%]
2c 3-dibenzofuryanyl 24.1 35 20 26.5
3 A 57
4c 4-phenylthiophenyl 6.31 9 30 7.06
4 A 89
7c 4-diphenylaminophenyl 25.3 35 90 21.1
2 B 94
8c 3-(N-ethyl)-carbazole 9.41 12.5 60 9.83
21/2 C + C1 90
10c 4-methoxy-1-naphthyl 15.1 23 30 17.4
1 C + C2 97
11c 4-morpholinophenyl 8.00 15 90 8.82
1 A 65
12c 1-pyrenyl 8.79 7.8.sup.1) 90
8.44.sup.2) 2 B 23
14c 3,4-ethylenedioxy-2-thienyl 5.48 9.0 60
7.18 2 A 76
.sup.1) + 10 ml H.sub.2 O; 2) + 10 ml H.sub.2 O
Workup
A: Excess hydrazine is removed by distillation, and then the mixture is
acidified with diluted HCl to pH 3. The product is then extracted with
CH.sub.2 C.sub.1.sub.2. The desired acid is purified by silica gel column
chromatography using a CH.sub.2 Cl.sub.2 -MeOH mixture as eluent.
B: Excess hydrazine is removed by distillation, and then the mixture is
acidified with diluted HCl. The product is then extracted with CH.sub.2
Cl.sub.2. The desired acid is purified by silica gel column chromatography
using a CH.sub.2 Cl.sub.2 -acetone mixture as eluent.
C: Excess hydrazine is removed by distillation, and then the mixture is
acidified with diluted HCl. The product is then extracted with CH.sub.2
Cl.sub.2. Then, CH.sub.2 Cl.sub.2 is removed by distillation.
C1: 9.18 g of a brownish solid are obtained as a crude product. This
product is used for the next reaction step without further purification.
C2: 13.8 g of a white solid are obtained.
Example 2d
13.6 g (56.7 mmol) of the product obtained in ex. 2b are treated with 6.70
g (59.7 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, and then the solvent is removed by evaporation. After drying under
an atmosphere of reduced pressure, the obtained solid is mixed with 12.8 g
(56.7 mmol) of the product obtained in ex. 2c and 110 ml of acetic
anhydride and thereafter heated to reflux for one hour. After removal of
acetic anhydride by evaporation under an atmosphere of reduced pressure,
the resulting yellow solid is washed with acetone, affording 11.0 g (45%)
of a yellow solid.
Example 3d
41.8 g (232 mmol) of the product obtained in ex. 3b are treated with 27.7 g
(247 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, and then the solvent is removed by evaporation. After drying under
an atmosphere of reduced pressure, the obtained solid is mixed with 39.5 g
(235 mmol) of p-methoxyphenylacetic acid (commercially available, corr. to
ex. 3c, 99% purity) in 460 ml of acetic anhydride and then heated to
reflux for 1.5 hours. Thereafter, acetic anhydride is removed by
evaporation in an atmosphere of reduced pressure. The resulting solid is
then washed with a hexane-acetone mixture, affording 74.3 g of an orange
solid (100%).
Example 4d
4.44 g (17.2 mmol) of the product obtained in ex. 2b are treated with 2.03
g (18.0 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the residue
under an atmosphere of reduced pressure, the obtained solid is mixed with
4.20 g (17.2 mmol) of the product obtained in ex. 4c in 35 ml of acetic
anhydride and heated to reflux for 1.5 hours. After removal of acetic
anhydride by evaporation in an atmosphere of reduced pressure, the
resulting solid is washed with MeOH. The desired product is purified by
silica gel column chromatography using CH.sub.2 Cl.sub.2 -hexane mixture
as eluent. 3.38 g of a yellow solid are obtained (42%).
Example 5d
4.22 g (20.1 mmol) of the product obtained in ex. 5b are treated with 2.37
g (21.1 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the residue
under an atmosphere of reduced pressure, the obtained solid is mixed with
3.95 g (20.1 mmol) of homoveratric acid (commercially available,
corresponding to ex. 5c) in 40 ml of acetic anhydride and heated to reflux
for 3.5 hours. After removal of acetic anhydride by evaporation in an
atmosphere of reduced pressure, the desired product is purified by silica
gel column chromatography using CH.sub.2 Cl.sub.2 as eluent. 3.23 g of an
orange solid are obtained (44%).
Example 6d
1.97 g (10.2 mmol) of the product obtained in ex. 6b are treated with 1.23
g (11.0 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying under an
atmosphere of reduced pressure, the obtained solid is mixed with 1.91 g
(10.3 mmol) of p-dimethylaminophenylacetic acid (commercially available,
corr. to ex. 6c) in 20 ml of acetic anhydride and heated to reflux for 1.5
hours. After removal of acetic anhydride by evaporation in an atmosphere
of reduced pressure, the desired product is purified by silica gel column
chromatography using hexane-CH.sub.2 Cl.sub.2 mixture as eluent. 1.39 g of
a dark red solid are obtained (41%).
Example 7d
18.9 g (59.4 mmol) of the product obtained in ex. 7b are treated with 7.00
g (62.4 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the residue
under an atmosphere of reduced pressure, the obtained solid is mixed with
18.1 g (59.7 mmol) of the product obtained in ex. 7c in 120 ml of acetic
anhydride and heated to reflux for 1.5 hours. After removal of acetic
anhydride by evaporation in an atmosphere of reduced pressure, the
resulting solid is washed with acetone. 24.3 g of a dark red solid are
obtained (70%).
Example 8d
8.40 g (31.4 mmol) of the product obtained in ex. 8b are treated with 3.73
g (33.3 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying under an
atmosphere of reduced pressure, the obtained solid is mixed with 8.00 g
(31.6 mmol) of the product obtained in ex. 8c in 60 ml of acetic anhydride
and heated to reflux for 7 hours. After removal of acetic anhydride by
evaporation in an atmosphere of reduced pressure, the resulting solid is
dissolved in CH.sub.2 Cl.sub.2, and then purified by silica gel column
chromatography using CH.sub.2 Cl.sub.2 -hexane mixture as eluent. 7.92 g
of a red solid are obtained (52%). by silica gel column chromatography
using hexane-ethyl acetate mixture as eluent. 20.9 g of slightly brownish
oil is obtained (92%).
Example 9d
10.3 g (51.5 mmol) of the product obtained in ex. 9b are treated with 6.04
g (53.8 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the
obtained residue under an atmosphere of reduced pressure, the obtained
solid is mixed with 9.36 g (50.3 mmol) of 1-naphthylacetic acid
(commercially available, corr. to ex. 9c) in 100 ml of acetic anhydride
and heated to reflux for 14 hours. After removal of acetic anhydride by
evaporation under an atmosphere of reduced pressure, the resulting solid
is dissolved in CH.sub.2 Cl.sub.2. This mixture then is treated using
silica gel column chromatography with a CH.sub.2 Cl.sub.2 -hexane mixture
as eluent to obtain 5.47 g of a yellow solid (31%)
Example 10d
14.6 g (63.3 mmol) of the product obtained in ex. 1Ob are treated with 7.36
g (65.6 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the
obtained residue under an atmosphere of reduced pressure, the obtained
solid is mixed with 13.6 g (62.9 mmol) of the product obtained in ex. 10c
in 130 ml of acetic anhydride and heated to reflux for 2 hours. After
removal of acetic anhydride by evaporation under an atmosphere of reduced
pressure, the resulting solid is dissolved in CH.sub.2 Cl.sub.2. This
mixture then is treated using silica gel column chromatography with a
hexane-ethyl acetate mixture as eluent to obtain 16.4 g of a brownish
orange solid (63%).
Example 11d
4.95 g (20.8 mmol) of the product obtained in ex. 11b are treated with 2.49
g (22.2 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the
obtained residue under an atmosphere of reduced pressure, the obtained
white solid is mixed with 4.61 g (20.8 mmol) of the product obtained in
ex. 11c in 40 ml of acetic anhydride and heated to reflux for 1.5 hours.
After removal of acetic anhydride by evaporation under an atmosphere of
reduced pressure, the resulting yellow solid is washed with acetone and
then dissolved in CH.sub.2 Cl.sub.2. This mixture then is treated using
silica gel column chromatography with a CH.sub.2 Cl.sub.2 -acetone mixture
as eluent to obtain 6.41 g of a yellow solid (74%).
Example 12d
1.66 g (6.05 mmol) of the product obtained in ex. 12b are treated with 716
mg (6.38 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the thus
obtained residue under an atmosphere of reduced pressure, the obtained
solid is mixed with 1.56 g (6.00 mmol) of the product obtained in ex. 12c
in 12 ml of acetic anhydride and heated to reflux for 1.5 hours. After
removal of acetic anhydride by evaporation under an atmosphere of reduced
pressure, the resulting red solid is washed with acetone, thereafter
extracted with hot CHCl.sub.3 using a Soxhlet extractor. 2.13 g of a red
solid are obtained (71%).
Example 13d
2.51 g (10.0 mmol) of the product obtained in ex. 13b are treated with 1.17
g (10.4 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the thus
obtained residue under an atmosphere of reduced pressure, the obtained
solid is mixed with 1.70 g (10.1 mmol) of p-methoxyphenylacetic acid
(commercially available, corr. to ex. 3d) in 20 ml of acetic anhydride and
heated to reflux for 2 hours. After removal of acetic anhydride by
evaporation under an atmosphere of reduced pressure, the resulting solid
is then dissolved in CH.sub.2 Cl.sub.2. This mixture then is treated using
silica gel column chromatography with a hexane-ethyl acetate mixture as
eluent to obtain 160 mg of a red solid (4.2%).
Example 14d
3.58 g (16.7 mmol) of the product obtained in ex. 14b are treated with 1.90
g (16.9 mmol) of tert.-BuOK in MeOH to obtain the corresponding potassium
salt, then the solvent is removed by evaporation. After drying the
obtained residue under an atmosphere of reduced pressure, the obtained
solid is mixed with 3.33 g (16.6 mmol) of the product obtained in ex. 14c
in 30 ml of acetic anhydride and heated to reflux for 3 hours. After
removal of acetic anhydride by evaporation under an atmosphere of reduced
pressure, the resulting solid is dissolved in CH.sub.2 Cl.sub.2. This
mixture is treated using silica gel column chromatography with a CH.sub.2
Cl.sub.2 -hexane mixture as eluent to obtain 1.72 g of a brown solid
(27%).
Example 15d
1.80 g (8.62 mmol) of the product obtained in ex. 15 b are treated with
1.06 g (9.46 mmol) of tert.-BuOK in MeOH to obtain the corresponding
potassium salt, then the solvent is removed by evaporation. After drying
the thus obtained residue under an atmosphere of reduced pressure, the
obtained solid is mixed with 1.61 g (8.64 mmol) of 2-naphthylacetic acid
(commercially available, corr. to ex. 15c) in 20 ml of acetic anhydride
and heated to reflux for 3 hours. After removal of acetic anhydride by
evaporation under an atmosphere of reduced pressure, the resulting solid
is dissolved in CH.sub.2 Cl.sub.2. This mixture then is treated using
silica gel column chromatography with a CH.sub.2 Cl.sub.2 -hexane mixture
as eluent to obtain 0.36 g of a yellow solid (12%).
Example 16d
4.51 g (29.8 mmol) of 4-acetylaminophenyl glyoxylic acid (commercially
available) are treated with 3.46 g (30.8 mmol) of tert.-BuOK in MeOH to
obtain the corresponding potassium salt, then the solvent is removed by
evaporation. After drying the residue under an atmosphere of reduced
pressure, the obtained solid is mixed with 4.51 g (29.8 mmol) of
p-aminophenylacetic acid in 60 ml of acetic anhydride and heated to reflux
for two hours. After removal of acetic anhydride by evaporation in an
atmosphere of reduced pressure, the desired product is purified by silica
gel column chromatography using CH.sub.2 Cl.sub.2 -acetone mixture as
eluent, obtaining 0.56 g of a yellow-orange solid (5.3%).
Example 17d
2.81 g (10.0 mmol) of the potassium salt (obtained by: 2.44 g (10 mmol) of
the product obtained in ex. 1 b are treated with 1.23 g (11 mmol) of
tert.-BuOK in MeOH) of the product obtained in ex. lb are mixed with 1.82
g (9.82 mmol) of p-dimethylaminophenylacetic acid (commercially available,
corr. to ex. 6c) in 20 ml of acetic anhydride and heated to reflux for 2
hours. After removal of acetic anhydride by evaporation under an
atmosphere of reduced pressure, the resulting yellow solid is washed with
a CH.sub.2 Cl.sub.2 -hexane mixture, which afforded 3.18 g of a dark red
solid (84%).
Example 18d
4.25 g (15.2 mmol) of potassium salt (obtained by: 3.71 g (15.2 mmol) of
the product obtained in ex. lb are treated with 1.85 g (16.5 mmol) of
tert.-BuOK in MeOH) of the product obtained in ex. lb are mixed with 4.60
g (15.2 mmol) of the product obtained in ex. 7c in 30 ml of acetic
anhydride and heated to reflux for 1.5 hours. After removal of acetic
anhydride by evaporation under an atmosphere of reduced pressure, the thus
obtained resulting solid is dissolved in CH.sub.2 Cl.sub.2. This mixture,
then, is treated using silica gel column chromatography with a
hexane-CH.sub.2 Cl.sub.2 mixture as eluent. 6.12 g of a dark red solid are
obtained (79%).
Example 19d
9.85 g (30.1 mmol) of the product obtained in ex. 7b (97% pure) are treated
with 3.53 g (31.5 mmol) of tert.-BuOK in MeOH to obtain the corresponding
potassium salt, then the solvent is removed by evaporation. After drying
the thus obtained residue under an atmosphere of reduced pressure, the
obtained solid is mixed with 5.40 g (31.7 mmol) of p-chlorophenylacetic
acid (commercially available, corr. to 19c) in 60 ml of acetic anhydride
and heated to reflux for 1.5 hours. After removal of acetic anhydride by
evaporation under an atmosphere of reduced pressure, the resulting solid
is dissolved in CH.sub.2 Cl.sub.2. This mixture is treated using silica
gel column chromatography with a hexane-CH.sub.2 Cl.sub.2 mixture as
eluent to obtain 9.54 g of a dark red solid (70%).
Example 20d
6.97 g (22.0 mmol) of the product obtained in ex. 7b (97% pure) are treated
with 2.62 g (23.4 mmol) of tert.-BuOK in MeOH to obtain the corresponding
potassium salt, then the solvent is removed by evaporation. After drying
the thus obtained residue under an atmosphere of reduced pressure, the
obtained solid is mixed with 4.70 g (21.7 mmol) of the product obtained in
ex. 10c in 45 ml of acetic anhydride and heated to reflux for 2 hours.
After removal of acetic anhydride by evaporation under an atmosphere of
reduced pressure, the resulting solid is dissolved in CH.sub.2 Cl.sub.2.
This mixture then is treated using silica gel column chromatography with a
hexane-CH.sub.2 Cl.sub.2 mixture as eluent to obtain 6.52 g of a red solid
(60%).
Example 21d
8.30 g (28.0 mmol) of the potassium salt (obtained by: 8.0 g (28 mmol) of
the product obtained in ex. 4b are treated with 3.45 g (30.8 mmol) of
tert.-BuOK in MeOH) of the product obtained in ex. 4b are mixed with 6.04
g (27.9 mmol) of the product obtained in ex. 10 c in 60 ml of acetic
anhydride and heated to reflux for 2 hours. After removal of acetic
anhydride by evaporation under an atmosphere of reduced pressure, the
resulting solid is dissolved in CH.sub.2 Cl.sub.2. This mixture is treated
using silica gel column chromatography with a hexane-CH.sub.2 Cl.sub.2
mixture as eluent to obtain 7.56 g of a red solid (62%).
(B) Preparation of N-alkyldiarylmaleimides
General
4 mmol of the corresponding diarylmaleic anhydride of formula V and an
excess (>4 mmol per each amino group) of the corresponding amine are
heated to reflux in 20 ml of a mixture of toluene-DMF (3:1) for several
hours. After removal of the solvents in an atmosphere under reduced
pressure, the product is purified by column chromatography (silica gel
with CH.sub.2 Cl.sub.2 -hexane as eluent).
Example 22
A mixture of 20.02 g (80 mmol) of diphenylmaleic anhydride and 2.4 g (40
mmol) of 1,2-ethlenediamine in toluene-DMF (1:1, 300 ml) is heated to
reflux for 4 hours. After removal of the solvent mixture in an atmosphere
under reduced pressure, the obtained crude solid is washed twice with each
100 ml of acetone. After drying, 19.72 g (94%) of a lemon yellow solid are
obtained.
Example 23
4.4 g (10 mmol) of the product obtained in example 1d are treated with 310
mg of 1,2-ethlenediamine (5.2 mmol) in toluene-DMF (3:1, 50 ml) and heated
under reflux for 6 hours. After removal of the solvents in an atmosphere
under reduced pressure, the desired product is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 -haxane mixture as eluent).
TABLE 4
compounds of formula IV (R.sub.13 = R.sub.14 = R.sub.16 = R.sub.17)
Yield
example R.sub.13 R.sub.15 (%) Colour Mp. (.degree. C.)
22 phenyl 1,2-ethylene 94 lemon- >250
yellow
23 4-phenoxyphenyl 1,2-ethylene 92 Yellow 115.2-117.0
Example 24
4.4 g (10 mmol) of the product obtained in example 1d are treated with 6.0
g of 1,2-ethlenediamine (100 mmol) in toluene-DMF (3:1, 50 ml) and heated
to reflux for 3 hours. After removal of the solvents in an atmosphere
under reduced pressure, a yellowish-orange product is collected by column
chromatography (silica gel, ethylacetate as eluent). This compound is
treated with 1 ml acetic anhydride in 10 ml toluene at room temperature
for 23 hours. The desired product is purified by column chromatography
(silica gel, ethylacetate/hexane mixture as eluent).
Example 25
4.1 mmol of 3,4-diphenoxyphenyl maleic anhydride (from example 1d) and 41
of AcONH.sub.4 are heated to reflux in acetic acid (20 ml) overnight.
After condensation of the reaction mixture, the resulting solid is
filtered and washed with H.sub.2 O and MeOH. The is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 as eluent).
Example 26-28
Example 25 is repeated, however, in example 26
3,4-di(4-diphenylaminophenyl) maleic anhydride, in example 27
3,4-di(4-methoxy-1-naphthyl) maleic anhydride, and in example 28
3,4-diphenyl maleic anhydride are used.
TABLE 5
compounds of formula II
Ex- Yield
ample R.sub.9 R.sub.10 (%) Colour Mp. (.degree. C.)
25 4-phenoxyphenyl H 96 Yellow 242.5-244.8
26 4-diphenylaminophenyl H 68 Dark 244.3-246.5
Red
27 4-methoxy-1-naphthyl H 77 Orange 239.6-242.1
28 phenyl H 91 Pale 217.5-218.4
Yellow
Example 29
460 mg (1.1 mmol) of the product obtained in ex. 25 are treated with 47 mg
of NaH 1.2 mmol) in 5 ml of DMF at room temperature for 20 min. Into this
reaction mixture 1,3-dibromopropane (1.0 ml, 9.9 mmol) are added and the
mixture is stirred for one day at room temperature. After adding 20 ml of
H.sub.2 O, the reaction mixture is extracted with CH.sub.2 Cl.sub.2. The
combined CH.sub.2 Cl.sub.2 -extracts are treated using column
chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture as eluent).
Example 30
949 mg of 1-pyrenemethanol (4.00 mmol) is treated with 2.0 g (6.0 mmol)
CBr.sub.4 and 27 g (4.9 mmol) PPh3 in 40 ml CH.sub.2 Cl.sub.2 at room
temperature for three hours. 20 ml of an saturated aqueous NaHCO.sub.3
solution is added to the reaction mixture, then the reaction mixture is
extracted with CH.sub.2 Cl.sub.2. After removal of CH.sub.2 Cl.sub.2, the
residue is added to the potassium salt of the product obtained in ex. 25,
which is prepared from 1.98 g (4.57 mmol) of the product obtained in ex.
25 by treatment with 520 mg of tert.-BuOK (4.63 mmol) in 10 ml of DMF at
room temperature for 5 min. This mixture is stirred for one day at room
temperature. After adding 10 ml of H.sub.2 O, the reaction mixture is
extracted with CH.sub.2 Cl.sub.2. The extracts are then treated using
column chromatography (silica gel, hexane-Et.sub.2 O (10:1) mixture as
eluent).
TABLE 6
compounds of formula II
ex-
am- Yield Col-
ple R.sub.9 R.sub.10 (%) our Mp. (.degree. C.)
24 4-phenoxyphenyl 2-acetylaminoethyl 12 yel- 71.7-
low 75.0
29 4-phenoxyphenyl 3-bromopropyl 90 yel- 148.1-
low 152.1
30 4-phenoxyphenyl 1-pyrenylmethyl 49 yel- 203.5-
low 205.8
Example 31
A mixture of 5.00 g (20 mmol) of diphenylmaleic anhydride and 2.02 mg (22
mol) of cyclohexylamine are heated to reflux in a mixture of toluene (150
ml) and DMF (150 ml) for five hours. After removal of the solvent mixture
in an atmosphere under reduced pressure, 50 ml of methanol are added to
solidify the material. The product is collected by filtration, then washed
with methanol. Yield: 4.7 g (71%) of a lemon-yellow solid.
Similarly to the above mentioned examples the following compounds are
synthesized:
TABLE 7
compounds of formula II
example R.sub.9 R.sub.10 Yield(%) Colour
Mp. (.degree. C.)
31 phenyl cyclohexyl 71 lemon-yellow
159.6-160.3
32 phenyl 2-aminoethyl 65 Yellow
>250
33 phenyl isopropyl 80 lemon-yellow
135.3-137.3
34 phenyl 2-aminocyclohexyl 99 Yellow
158.5-160.1
35 phenyl allyl 62 Yellow
89.2-92.0
36 3,4-ethylenedioxy- cyclohexyl 78 Orange
102.1-104.2
2-thienyl
37 4-methoxyphenyl cyclohexyl 52 Yellow
96.7-100.4
38 1-naphthyl cyclohexyl 90 Yellow
103.2-108.8
39 4-phenoxyphenyl cyclohexyl 92 Greenish-yellow
183.9-186.1
40 4-dimethylamino- cyclohexyl 79 Dark red
229.9-232.0
phenyl
41 4-phenoxyphenyl isopropyl 86 Yellow
100.9-102.6
42 4-phenoxyphenyl tris(hydroxymethyl) 100 Yellow
148.3-150.6
methyl
43 4-diphenylamino- cyclohexyl 63 Reddish-orange
205.2-208.6
phenyl
44 4-methoxy-1- cyclohexyl 84 Yellowish-orange
151.0-155.2
naphthyl
45 4-acetylamino- cyclohexyl 90 Yellow
164.5-168.5
phenyl
46 4-diphenylamino- isopropyl 75 Orange
212.8-213.6
phenyl
47 3,4-dimethoxy- cyciohexyl 95 Orange
135.3-136.9
phenyl
48 4-phenoxyphenyl methyl 80 Yellow
134.2-136.4
49 4-phenoxyphenyl trans-4-aminocyclohexyl 29 Yellow
162.5-165.2
50 4-diphenylamino- 4-aminocyclohexyl 60 Reddish-orange
245.6-248.5
phenyl
TABLE 8
compounds of formula III
example R.sub.11 R.sub.12 R.sub.13 Yield(%) Colour
Mp. (.degree. C.)
51 4-phenoxyphenyl 4-dimethylamino- cyclohexyl 100 Red
80.2-84.1
phenyl
52 4-phenoxyphenyl 4-dimethylamino- stearyl 90 Orange
111.5-113.6
phenyl
53 4-methoxyphenyl 9-anthryl cyclohexyl 81 Yellowish-
183.2-186.1
orange
54 3-dibenzofuranyl 2/3-dibenzofuranyl isopropyl 58 Greenish-
218.0-222.2
yellow
TABLE 9
compounds of formula IV (R.sub.13 = R.sub.14 = R.sub.16 = R.sub.17)
Yield
example R.sub.13 R.sub.15 (%) Colour Mp (.degree. C.)
55 4-phenoxyphenyl trans-1,4-cyclo- 16 Yellow >250
hexylene
and example 56, yielding a reddish-orange compound of the formula
##STR33##
with a yield of 84%, and a melting point of >250.degree. C.
(C) Preparation of N-alkyldiarylmaleimides
General
The corresponding diarylmaleic anhydride (4 mmol) and the corresponding
amine (>4 mmol) are heated to reflux in acetic acid (20 ml) for several
hours. After removal of the solvents in an atmosphere under reduced
pressure, the product is purified by column chromatography (silica gel,
CH.sub.2 Cl.sub.2 -haxane mixture as eluent).
Example 57
280 mg (1.1 mmol) of diphenylmaleic anhydride are treated with 110 mg of
2,5-di-tert.-butyl-1,4-phenylenediamine (0.51 mmol) in acetic acid (5.0
ml) and heated to reflux for 3 hours. After removal of the solvents in an
atmosphere under reduced pressure, the desired product is purified by
column chromatography (silica gel, CH.sub.2 Cl.sub.2 as eluent).
Example 58
920 mg of diphenylmaleic anhydride (3.7 mmol) and 260 mg of
1,5-diaminonaphthalene (1.6 mmol) are refluxed in acetic acid (10 ml) for
three hours. After removal of the solvents in an atmosphere under reduced
pressure, the product is purified by column chromatography (silica gel,
CH.sub.2 Cl.sub.2 as eluent).
Example 59
920 mg of diphenylmaleic anhydride (3.7 mmol) and 140 mg of melamine (1.1
mmol) are heated to reflux in acetic acid (10 ml) for 14 hours. The
resulting solid is collected by filtration, and the product is purified by
column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane as eluent).
Yield: 60%, pale yellow compound, melting point 157.6-162.6.degree. C.
Example 60
similarly a compound of formula II with R.sub.9 =phenyl and R.sub.10
=3-(hydroxymethyl)phenyl is prepared.
Example 61
similarly a compound of formula II with R.sub.9 =4-phenoxyphenyl and
R.sub.10 =4-amino-2,5-dimethylphenyl is prepared.
Example 62
6.5 g (18 mmol) of the product obtained in ex. 60 are treated with 9.2 g of
CBr.sub.4 (28 mmol) in the presence of PPh.sub.3 (5.8 g, 22 mmol) in 100
ml of CH.sub.2 Cl.sub.2 at room temperature for 10 min. After adding 20 ml
of an saturated aqueous NaHCO.sub.3 solution, the reaction mixture is
extracted with CH.sub.2 Cl.sub.2. The combined extracts are then treated
using column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture
as eluent).
Example 63
340 mg (1.0 mmol) of 3,4,9,10-perylenetetracarboxylic dianhydride, 460 g
(2.1 mmol) of zinc acetate dihydrate and 1.1 g (1.1 mmol) of the product
obtained in ex. 60 are mixed in 4.0 g of imidazole and stirred at
160.degree. C. for 7 hours. Then the reaction mixture is extracted with
CH.sub.2 Cl.sub.2 and the combined extracts are treated using column
chromatography (silica gel, CH.sub.2 Cl.sub.2 -MeOH as eluent).
Example 64
560 mg (1.0 mmol) of the product obtained in ex. 61 are treated with 100 mg
of terephthaloyl chloride (0.51 mmol) in the presence of Et.sub.3 N (0.5
ml) in 10 ml of CH.sub.2 Cl.sub.2 at room temperature for two hours. The
resulting solid is filtered and washed first with MeOH, then CH.sub.2
Cl.sub.2, and thereafter with acetone. An insoluble yellow solid is
obtained.
TABLE 10
compounds of formula II
example R.sub.9 R.sub.10 Yield(%) Colour Mp.
(.degree. C.)
60 phenyl 3-(hydroxymethyl)phenyl 99 Yellow
141.5-142.3
61 4-phenoxyphenyl 4-amino-2,5-dimethylphenyl 76 Orange
202.6-204.4
62 phenyl 3-(bromomethyl)phenyl 60 Yellow
157.4-159.6
Similarly the following compounds of formula II are prepared:
TABLE 11
compounds of formula II
ex. R.sub.9 R.sub.10 Yield(%) Colour Mp.
(.degree. C.)
65 phenyl phenyl 75 Yellow
170.3-173.7
66 phenyl 2,6-diisopropylphenyl 94 Pale green-
217.3-222.9
nish-yellow
67 phenyl 4-phenoxyphenyl 86 Yellow
186.9-188.7
68 4-phenoxyphenyl 2,6-diisopropylphenyl 90 Yellow
202.8-205.2
69 4-diphenylaminophenyl 2,6-diisopropylphenyl 63 Red
165.0-167.5
70 4-phenoxyphenyl 2,6-dimethylphenyl 93 Yellow
239.0-240.9
71 4-phenoxypjhenyl phenyl 93 Yellow
175.6-178.9
72 4-phenoxyphenyl 2-chloropenyl 45 Yellow
184.0-186.4
73 4-phenoxyphenyl 2-methylphenyl 95 Yellow
204.4-207.1
74 4-phenoxyphenyl 2,6-dichlorophenyl 10 Yellow
189.5-191.8
77 4-phenoxyphenyl 2-amino-4,5-dimethylphenyl 64 Orange
97.6-99.8
78 4-phenoxyphenyl 2-phenylphenyl 58 Pale Yellow
170.7-173.8
79 4-diphenylaminophenyl 2-methylphenyl 75 Reddish-
249.9-252.8
orange
80 4-phenoxyphenyl 2-phenoxyphenyl 44 Yellow
194.6-196.2
81 4-phenoxyphenyl 4-aminocarbonylphenyl 65 Yellowish-
189.1-190.1
orange
82 4-methoxy-1-naphthyl 2-phenoxyphenyl 7 Red
140.1-143.3
83 4-diphenylaminophenyl 2-phenoxyphenyl 7 Red
140.1-143.3
84 3-(N-ethyl)-carbazole 2,6-dimethylphenyl 100 Reddish-
>250
orange
85 4-phenylthiophenyl 2,6-dimethylphenyl 71 Orange
178.6-180.4
87 4-morpholino- 2,6-dimethylphenyl 87 Reddish-
>250
phenyl orange
88 4-phenoxyphenyl 1-pyrenyl 71 Yellow
>250
89 2-naphthyl 2,6-dimethylphenyl 95 Yellow
189.7-190.7
91 1-pyrenyl 2,6-dimethylphenyl 100 Orange
>250
92 4-methoxy-1-naphthyl 2,6-dimethylphenyl 100 Orange
149.7-151.6
TABLE 12
compounds of formula IV (R.sub.13 =R.sub.14 =R.sub.16 =R.sub.17)
example R.sub.13 R.sub.15 Yield (%) Colour Mp.
(.degree. C.)
57 phenyl 2,5-di-tert.-butyl- 70 greenish-yellow
>250
1,4-phenylene
58 phenyl 1,5-naphthylene 84 Pale yellow >250
63 4-phenoxyphenyl perylene derivative 22 Reddish-orange
>250
of formula
##STR34##
64 4-phenoxyphenyl diamide of formula 54 Yellow >250
##STR35##
Similarly the following compounds of formula IV are obtained:
TABLE 13
compounds of formula IV (R.sub.13 = R.sub.14 = R.sub.16 = R.sub.17)
example R.sub.13 R.sub.15 Yield (%) Colour
Mp. (.degree. C.)
75 4-phenoxyphenyl 2,5-dimethyl-1,4-phenylene 21 Yellow
>250
76 4-phenoxyphenyl 4,5-dimethyl-1,2-phenylene 8 Yellow
166.1-168.7
90 4-phenoxyphenyl a biradical of the formula 57 Yellow
220.7-221.3
##STR36##
Similarly the following compounds of formula III are obtained:
TABLE 14
compounds of formula III
example R.sub.11 R.sub.12 R.sub.13 Yield (%) Colour
Mp. (.degree. C.)
86 4-phenoxyphenyl 4-diphenylamino- 2,6-dimethyl- 87 Orange
231.1-231.9
phenyl phenyl
93 4-chlorophenyl 4-diphenylamino- 2,6-dimethyl- 92 Reddish-
115.7-117.1
phenyl phenyl orange
94 4-methoxy-1- 4-diphenylamino- 2,6-dimethyl- 90 Red
142.3-144.6
naphthyl phenyl phenyl
95 4-methoxy-1- 4-phenylthio- 2,6-dimethyl- 83 Orange
99.5-100.6
naphthyl phenyl phenyl
Example 96
7.5 g (30 mmol) of diphenylmaleic anhydride and 750 mg (15 mmol) of
hydrazine hydrate are heated to a temperature of 120.degree. C. in
o-dichlorobenzene for 16 hours. After the reaction mixture is allowed to
cool to room temperature, 100 ml of hexane are added and the obtained
precipitate is collected by filtration. After drying, 4.6 g (62%) of a
pale yellow solid are obtained. Melting point: >250.degree. C.
Example 97
(a) 20 g (78 mmol) of diphenylmaleic anhydride in acetone (600 ml) are
irradiated by 400 W high pressure Hg lamp in the presence of iodine (85
mg, 0.34 mmol) for 21 hours. The resulting pale yellow solid is filtered
and washed with acetone. 7.9 g of pale yellow solid
9,10-phenanthrenedicaboxylic anhydride are obtained (41 %). (b) 500 mg
(2.0 mmol) of 9,10-phenanthrenedicaboxylic anhydride are treated with 390
mg (2.0 mmol) of 2,6-diisopropylaniline (90%) in 10 ml of acetic acid and
heated to reflux for 6 hours. After addition of H.sub.2 O, the resulting
solid is filtered and washed with H.sub.2 O and MeOH. The product is
purified by column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane
mixture as eluent). 220 mg of a pale yellow solid are obtained (28%).
Melting point: >250.degree. C.
Example 98
3.74 g (15.1 mmol) of 9,10-phenanthrenedicaboxylic anhydride (from ex. 97
(a)) are treated with 3.66 g (30.2 mmol) of 2,6-dimethylaniline in 30 ml
of acetic acid and heated to reflux for 30 hours. After addition of
H.sub.2 O, the resulting solid is filtered and washed with H.sub.2 O and
MeOH. The product is purified by column chromatography (silica gel,
CH.sub.2 Cl.sub.2 -hexane mixture as eluent). 3.06 g of a pale yellow
solid are obtained (58%). Melting point: 198.7-199.1.degree. C.
Example 99
(a) 1.01 g (4.08 mmol) of 9,10-phenanthrenedicaboxylic anhydride (from ex.
97 (a)) are treated with 6.34 g (82.3 mmol) of ammonium acetate in 12 ml
of acetic acid and heated to reflux for 50 hours. After addition of
H.sub.2 O, the resulting solid is filtered and washed first with H.sub.2
O, then MeOH, and thereafter with CH.sub.2 Cl.sub.2. The obtained pale
yellow solid is treated with 4.56 g (20.9 mmol) of
di-tert.-butyl-dicarbonate ("(BOC).sub.2 O") in the presence of
p-dimethylaminopyridine DMF for one day. After addition of H.sub.2 O, the
resulting solid is filtered and washed with H.sub.2 O and then MeOH. 793
mg of N-BOC-9,10-phenanthrenedicaboximide are obtained after purification
using column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture
as eluent).
(b) 403 mg (1.16 mmol) of this N-BOC derivative are treated with 10 ml of
50% CH.sub.2 Cl.sub.2 solution of trifluoroacetic acid at room temperature
for 45 min. The reaction mixture is neutralized with 10 ml of an saturated
aqueous NaHCO.sub.3 solution and the resulting solid is filtered. Washing
with MeOH and CH.sub.2 Cl.sub.2 afforded the pure desired product. 230 mg
of a pale yellow solid are obtained (80% from the N-BOC derivative).
Melting point: >250.degree. C.
Example 100
To 30 g (230 mmol) of AlCl.sub.3 in CH.sub.2 Cl.sub.2 (75 ml) are added
dropwise to a mixture of 17 g (100 mmol) of 4-phenoxybenzene and 21 g (150
mmol) of ethyl chloroglyoxylate in CH.sub.2 Cl.sub.2 (75 ml) at ice-bath
temperature over one hour. After completion of addition, the mixture is
gradually warmed up to room temperature and stirred overnight. Then, the
reaction mixture is poured onto ice. The aq. solution is acidified to pH 3
with a HCl aq. solution. Then the reaction mixture is extracted with
CH.sub.2 Cl.sub.2. Thereafter the extract is dried over anhydrous
MgSO.sub.4. The product is further purified by silica gel column
chromatography using CH.sub.2 Cl.sub.2 -hexane mixture as eluent. 11 g of
a white solid are obtained (31% based on 4-phenoxybenzene in addition to
4-phenoxyphenyl glyoxylic acid ethyl ester (37%). 11 g (29 mmol) of the
white solid, a diester, are hydrolyzed with 3.7 g (89 mmol) of NaOH (96%)
in 70 ml of H.sub.2 O and 70 ml of EtOH and heated to reflux for 5 hours.
The mixture is acidified to pH 3, and then the product, a diacid, is
extracted with CH.sub.2 Cl.sub.2. 9.2 g of an oil are obtained as a crude
product. This product is used for the next reaction without further
purification. 3.2 g of this oil are treated with 2.5 g (22 mmol) of
tert.-BuOK in MeOH to obtain the corresponding potassium salt, and then
the solvent is removed by evaporation. After drying in an atmosphere under
reduced pressure, the obtained solid is mixed with 3.4 g (21 mmol) of
p-methoxyphenylacetic acid in 30 ml of acetic anhydride and heated to
reflux for 6 hours. After removal of acetic anhydride by evaporation in an
atmosphere under reduced pressure, the product is purified by silica gel
column chromatography using CH.sub.2 Cl.sub.2 -hexane mixture as eluent.
This product is treated with 2 ml (23 mmol) of isopropylamine in
toluene-DMF (3:1, 10 ml) for 4 hours. After removal of the solvents under
reduced pressure, the product is purified by column chromatography (silica
gel, CH.sub.2 Cl.sub.2 -haxane mixture as eluent). 69 mg of a yellow solid
is obtained (1.0% from the corresponding diacid). Melting point:
86.0-89.1.degree. C.
Example 101
(a) 3,6-Diphenoxy-9,10-phenanthrenedicarboxylic anhydride: 4.9 g (11 mmol)
of 3,4-di(4-phenoxyphenyl) maleic anhydride (obtained from ex. 1d) in
acetone (600 ml) are irradiated by 400 W high pressure Hg lamp in the
presence of iodine (43 mg, 0.17 mmol) for 68 hours. After removal of
acetone, the resulting solid is filtered and washed with acetone. The
product is purified by column chromatography (silica gel, CH.sub.2
Cl.sub.2 -hexane mixture as eluent). 1.4 g of a yellow solid are obtained
(30%).
(b) 450 mg (1.0 mmol) of 3,6-diphenoxy-9,10-phenanthrenedicarboxylic
anhydride are treated with 260 mg (2.1 mmol) of 2,6-dimethylaniline in 10
ml of acetic acid and heated to reflux for 7 hours. After addition of
H.sub.2 O, the resulting solid is filtered and washed with H.sub.2 O. The
product is purified by column chromatography (silica gel, CH.sub.2
Cl.sub.2 -hexane mixture as eluent). 550 mg of a yellow solid are obtained
(99%). Melting Point: 223.7-224.5.degree. C.
Example 102
(a) 4-bromomethyl Phenyl Acetic Acid
A mixture of 50 g (0.33 mol) of 4-methylphenyl acetic acid, 62 g (0.35 mol)
of N-bromo-succinimide, 200 ml of carbon tetrachloride and 0.1 g of
2,2-azobis(isobutyronitrile) are placed in a 500 ml flask and heated to
reflux with stirring for 4 hours. After the reaction mixture is cooled to
room temperature, it is poured into 500 ml of water. The obtained
precipitate is filtered off, and then washed with water. After drying
under an atmosphere of reduced pressure, 55 g of a white powder are
obtained (72%).
(b) Phosphonium Salt
A mixture of 11.45 g (0.05 mol) of 4-bromomethyl phenyl acetic acid, 13.1 g
(0.05 mol) of triphenyl phosphine and 500 ml of toluene is refluxed for 2
hours. The reaction mixture is cooled down to room temperature, and the
thus obtained precipitates are collected by filtration and subsequently
washed with hot hexane. After drying, 21.86 g of a phosphonium salt are
obtained (89%).
(c) 4-stilbene Acetic Acid
At room temperature, 4.91 g (0.01 mol) of the above obtained phosphonium
salt, 1.17 g (0.011 mol) of benzaldehyde, 211 mg (0.8 mmol) 18-crown-6 and
1.68 g (0.03 mol) of KOH are added to 40 ml of dichloromethane and stirred
for 18 hours. After being acidified with 1 M HCl, the dichloromethane is
separate off and removed off in atmosphere under reduced pressure. The
product is purified by column chromatography (silica gel, CH.sub.2
Cl.sub.2 -methanol mixture as eluent). After drying, 4-stilbene acetic
acid is obtained quantitatively.
(d) 3.17 g (10 mmol) of triphenylamino glyoxylic acid is placed in a flask
containing 1.3 g (11.6 mmol) of tert.-BuOK and 30 ml of methanol. The
mixture is heated up to reflux for 1 hour. Then the methanol is removed to
give the corresponding triphenylglyoxylic acid potassium salt
quantitatively. To the obtained triphenylglyoxylic acid potassium salt
2.38 g (10 mmol) of 4-stilbene acetic acid and 30 ml of acetic anhydride
are added and heated up to 130.degree. C. for 2 hours. After the reaction
mixture is cooled to room temperature, acetic anhydride is removed in an
atmosphere under reduced pressure and the product is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture as eluent).
2.3 g of the corresponding red solid maleic anhydride are obtained (44%).
(e) A mixture of 2.08 g (4 mmol) of this maleic anhydride, 2.12 g (12 mmol)
of 2,6-diisopropylaniline and 25 ml of acetic acid is heated up to
150.degree. C. for 12 hours. After the acetic acid is removed in an
atmosphere under reduced pressure, the product is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture as eluent).
2.45 g of a red solid maleimide of formula XI
##STR37##
are obtained (90%).
Example 103
Example 102 is repeated except that 2-pyridinecarboxyaldehyde is used at
the stage of the Wittig reaction and a red solid compound of formula XII
##STR38##
is obtained.
Example 104
Example 102 is repeated except that 2-thiophenecarboxyaldehyde is used at
the stage of the Wittig reaction and a red solid compound of formula XIII
##STR39##
is obtained.
Example 105
Example 102 is repeated except that p-tolylaldehyde is used at the stage of
the Wittig reaction and a red solid compound of formula XIV
##STR40##
is obtained.
Example 106
Example 102 is repeated except that 4-chlorobenzdehyde is used at the stage
of the Wittig reaction and a red solid compound of formula XV
##STR41##
is obtained.
Example 107
Example 102 is repeated except that 4-phenoxyphenylglyoxylic acid is used
for the preparation of maleic anhydride to give a yellow fluorescent solid
compound of formula XVI
##STR42##
Example 108
Example 102 is repeated except that 4-cyanobenzaldehyde is used at the
stage of the Wittig reaction and a red solid compound of formula XVII
##STR43##
is obtained.
Example 109
Example 102 is repeated except that 4-methoxybenzaldehyde is used at the
stage of the Wittig reaction and a red solid compound of formula XVIII
##STR44##
is obtained.
Example 110
A mixture of 5 g (20 mmol) of diphenylmaleic anhydride and 1.14 g (10 mmol)
of 1,4-diaminocyclohexane are heated to reflux in a mixture of 150 ml
toluene and 50 ml of DMF for eight hours. After removal of the solvent
mixture in an atmosphere under reduced pressure, the obtained crude solid
is washed twice with each 100 ml of acetone. After drying, 2.26 g (39%) of
a lemon yellow solid is obtained.
Example 111
Photostability Testing of the Compounds in High-impact Polystyrene (HIPS)
1. Preparation of samples for the photostability testing:
1.1 Formulation comprising of the following components is prepared:
HIPS (FINA 825 from FINA Oil and chemical Co,; 99.9 wt- %
melt flow index is 8.0 on ASTM D-1238)
compound 0.1 wt- %
1.2 Dry tumbling is carried out for the above formulation for 15 min.
1.3 HIPS plates are prepared with an injection-molding machine at
220.degree. C. The dwell time is 3 min.
1.4 The plates are exposed to a Xenon-lamp using Fade-O-meter (Model
WEL-15X-HC-B.EC, Suga Co. ltd.) under the following condition:
.cndot. Xe-lamp power 0.35 W/m.sup.2 at 340 nm
.cndot. Black panel temperature 63.degree. C.
.cndot. Humidity (relative) 50%
.cndot. Mode no-rain
1.5 Photostability after 100-hour exposure is evaluated in terms of
photoluminescence intensity and color change (.DELTA.E.sub.ab and blue
scale).
2 Results
The results are summarized in the table below.
Plates prepared from maleimides obtained in ex. 39 and ex. 79 are found to
retain strong photoluminescence intensities, even after 100-hour
weathering test. The above compounds display color change
(.DELTA.E.sub.ab), corresponding to the results of Gray Scale evaluation
(the maximum scale is "5").
TABLE 15
Results of photostability tests
Before After 100-hour exposure
plates ob- exposure Photolu-
tained with Photolumi- mines-
compounds nescence cence Gray
of example: Color intensity intensity .DELTA.E.sub.ab scale
39 greenish yellow 928.6 721.1 5.21 5
24 yellow 876.2 450.1 11.90
73 yellow 668.0 484.9 5.18
79 reddish orange 504.7 483.7 0.50 5
46 orange 548.4 525.7 1.55
44 yellowish orange 485.9 364.8 2.43
27 orange 432.4 391.3 3.59
82 orange 372.2 345.8 2.22
36 orange 879.2 657.1 11.43
37 yellow 973.4 684.7 7.53
38 yellow 154.9 126.0 1.92
45 yellow 940.3 685.0 6.53
47 orange 682.0 561.3 4.88
84 reddish orange 718.6 673.0 1.70
85 orange 981.1 803.3 4.10
1.2 The above formulation is applied to a disperser (LAU GmbH, model BA-S
20 K) for two hours to achieve a homogeneous dispersion of the pigment.
1.3 The dispersion obtained is applied on a transparent polyester substarte
film using a blade to give ca. 100 .mu.m thick of the painted layer.
1.4 The film is exposed to a Xe-lamp using a Fade-Ometer (Model
WEL-15-X-HC-B.EC, Suga Co.Ltd.) under the following condition:
.cndot. Xe-lamp power 0.35 W/m.sup.2 at 340 nm
.cndot. black panel temperature 63.degree. C.
.cndot. humidity (relative) 50%
.cndot. mode no-rain
1.5 Photostability after 100-hour exposure is evaluated in terms of
photoluminescence intensity and color change (.DELTA.E.sub.ab and blue
scale).
2 Results
The results are summarized in the Table below
The following compounds show photoluminescence intensities stronger than
the commercial products, i.e. Radiant, even after 100-hour weathering
test: ex. 39, 41, 25, 24, 70, 72, 73, 74, 80, and 45.
TABLE 16
Results of photostability tests in NC-ink formulation
Before After 100-hour exposure
plates ob- exposure Photolu-
tained with Photolumi- mines-
compounds nescence cence Blue
of example: Color intensity intensity .DELTA.E.sub.ab scale
39 greenish yellow 3203 2609 8.21 5-6
41 yellow 2358 1413 5.39 4-5
25 yellow 2441 1673 2.57 5-6
24 yellow 1973 968 11.18 5-6
70 yellow 2748 2287 4.05 <6
72 yellow 2914 1860 5.18 5-6
73 yellow 2681 2122 4.67 5
74 yellow 3041 2147 4.46 6
80 yellow 1663 1632 0.73 6
45 yellow 1673 1109 5.47 6
Radiant Y. 2093 115 28.98 <3
Radiant R. 1640 116 25.44 <3
Radiant O. 1267 32 25.07 <3
Example 113
Photostability Testing of the Compounds in Linseed Oil Ink Formulation
1. Preparation of the ink formulation:
1.1 Formulation comprising of the following components is prepared:
linseed oil: 75.0 wt.-%
compound: 25.0 wt.-%
1.2 The above formulation is applied to an Automatic Hoover Muller (from
Toyo Seiki Co.) for three minutes to achieve a homogeneous dispersion of
the pigment.
1.3 The dispersion obtained is applied on a white paper substrate using a
blade to give a 100 .mu.m thick painted layer.
1.4 The film is exposed to a Xe-lamp using a Fade-Ometer (Model
WEL-15-X-HC-B.EC, Suga Co.Ltd.) under the following condition:
.cndot. Xe-lamp power 0.35 W/m.sup.2 at 340 nm
.cndot. black panel temperature 63.degree. C.
.cndot. humidity (relative) 50%
.cndot. mode no-rain
1.5 Photostability after 100-hour exposure is evaluated in terms of
photoluminescence intensity and color change (.DELTA.E.sub.ab and blue
scale).
2 Results
The results are summarized in the Table below.
The following compounds show photoluminescence intensities stronger than
the commercial products, i.e. Radiant, even after 100-hour weathering
test: compounds from ex. 39, 41, 25, 70, and 80. In addition, these
compounds display a color change .DELTA.E.sub.ab superior to the state of
the art compounds.
TABLE 17
Results of photostability tests in linseed oil ink formulation
Before After 100-hour exposure
plates ob- exposure Photolu-
tained with Photolumi- mines-
compounds nescence cence Blue
of example: Color intensity intensity .DELTA.E.sub.ab scale
39 greenish yellow 4124 3971 2.35 6
41 yellow 3209 3511 3.16 6
25 yellow 3421 2680 2.44 6
70 yellow 3624 3181 3.48 6
80 yellow 2225 1889 1.59 6
Radiant Y. 5217 1616 56.79 <3
Radiant R. 3227 2159 40.46 <3
Radiant O. 4386 1237 45.90 <3
Example 114
Photostability Testing of the Compounds in PMMA
1. Preparation of samples for the photostability testing:
1.1 Formulation comprising of the following components is prepared:
PMMA (Sumiplex LG from Sumitomo Chemical Co.;
melt flow index is 10 g/10 min on JlS-K7210): 99.9 wt.-%
compound: 0.1 wt.-%
1.2 Dry tumbling is carried out for the above formulation for 15 minutes.
1.3 PMMA plates are prepared with an injection-molding machine at
220.degree. C. The dwell time is three minutes.
1.4 The plate is exposed to a Xe-lamp using a Fade-Ometer (Model
WEL-15-X-HC-B.EC, Suga Co.Ltd.) under the following condition:
.cndot. Xe-lamp power 0.35 W/m.sup.2 at 340 nm
.cndot. black panel temperature 63.degree. C.
.cndot. humidity (relative) 50%
.cndot. mode no-rain
1.5 Photostability after 100-hour exposure is evaluated in terms of
photoluminescence intensity and color change (.DELTA.E.sub.ab and blue
scale).
2 Results
The results are summarized in the Table below. Compounds of ex. 39, 70, 80,
79, and 46 are found to retain strong photoluminescence intensity, even
after 100-hour weathering test. The above mentioned compounds exhibit a
small color change (.DELTA.E.sub.ab), corresponding to the results of a
Gray Scale evaluation (maximum scale="5"). The comparative examples from
Radiant are evaluated only using a Gray Scale, indicating that the results
are inferior to the inventive compounds.
TABLE 18
Results of photostability tests in PMMA
Before After 100-hour exposure
plates ob- exposure Photolu-
tained with Photolumi- mines-
compounds nescence cence Gray
of example: color intensity intensity .DELTA.E.sub.ab scale
39 greenish yellow 752 607 6.75 4-5
70 yellow 698 523 7.66 4-5
80 yellow 400 286 6.14 4-5
79 reddish orange 331 319 0.53 5
46 orange 393 371 0.73 5
Radiant Y. 3-4
Radiant R. 2
Radiant O. 1-2
Example 115
On an ITO glass substrate (made by Geomatech Co. Ltd., ITO film thickness
200 nm, sheet resistance 10 .OMEGA./cm.sup.2), a diamine represented by
the following formula
##STR45##
is deposited as a hole transporting substance by vacuum evaporation under a
vacuum of 6.65.times.10.sup.-4 Pa (5.0.times.10.sup.-6 Torr) and at a
depositing rate of 0.05 nm/sec to a membrane thickness of 50 nm.
Then, on the hole transporting layer thus prepared, the product obtained in
ex. 37 is deposited under a depositing condition of 6.65.times.10.sup.-4
Pa (5.0.times.10.sup.-6 Torr) and 0.05 nm/sec to a membrane thickness of
50 nm to form a light-emitting layer.
Then, on this light-emitting layer, firstly lithium is doped with the above
compound at a rate of 0.015 nm/s to form a 1 nm-thick layer and
subsequently aluminum as cathode are deposited on it to a film thickness
of 200 nm.
By using the ITO side as the anode and the magnesium side as the cathode, a
bias of 20 V is applied to the above element. A luminescence showing a
luminance of 248 cd/m.sup.2 (using Luminometer LS-110 manufactured by
Minolta Co, Ltd) is obtained as the average value of the five elements.
Examples 116-125
Example 115 is repeated, except the following light-emitting compounds are
employed. The results are summarized in Table 19 below together with the
results of Example 115.
TABLE 19
Light-emitting compound Luminance
Example obtained from example: .lambda..sub.EL (nm) (cd/m.sup.2)
115 37 556 248
116 22 514 60
117 38 552 126
118 25 553 14
119 69 628 152
120 70 551 150
121 79 633 81
122 80 554 120
123 46 618 233
124 55 554 61
125 102 641 350
Example 126
Void Detection
A waterborne primer based on acrylic latex is prepared according to the
following formulation:
Composition wt.- %
1) Demineralized water 3.10
2) Methylcarbitol.sup.a) 5.00
3) Orotan 165.sup.b) 0.82
4) Triton CF 10.sup.c) 0.29
5) Drew Plus TS 4380.sup.d) 0.28
6) Acrysol RM 8.sup.e) 0.60
7) Bayferrox 130 M.sup.f) 5.72
8) Millicarb.sup.9) 17.40
9) fluorescent agent
10) Butyldigykol 3.67
11) Maincote HG-54.sup.h) (41.5% supply form) 58.70
12) Texanol.sup.i) 1.50
13) Di-butylphthalate.sup.k) 1.50
14) Sodium nitrite.sup.l) (13.8% in dem. water) 0.80
15) Drew T 4310.sup.m) 0.32
16) ammonia(25%) 0.30
Total 100.0
solids: 47%; pH: 8-8.5
wherein:
.sup.a) Methylcarbitol: di-ethylene-glykolmonomethylether (from Union
Carbide);
.sup.b) Orotan 165: dispersing agent (Rohm and Haas Company);
.sup.c) Triton CF 10: non - ionic wetting agent (Rohm and Haas Comp.);
.sup.d) Drew Plus TS 4380: defoamer (Drew Chem. Corp.)
.sup.e) Acrysol RM 8: non - ionic thickener (Rohm and Haas Comp.);
.sup.f) Bayferrox 130 M: red iron oxide pigment (Bayer AG);
.sup.g) Millicarb: calcium carbonate (Omya);
.sup.h) Maincote HG-54: acrylic dispersion (Rohm and Haas Comp.);
.sup.i) Texanol. coalescent (Eastman Chem. Prod., Inc.);
.sup.k) Di - butylphthalate: plastisizer (Eastman Chem. Prod., Inc.);
.sup.l) sodium nitrite flash rust inhibitor (Fluka);
.sup.m) Drew T 4310: non - ionic defoamer (Drew Chem. Corp.)
wherein:
a) Methylcarbitol: di-ethylene-glykolmonomethylether (from Union Carbide);
b) Orotan 165: dispersing agent (Rohm and Haas Company); c) Triton CF 10:
non-ionic wetting agent (Rohm and Haas Comp.); d) Drew Plus TS 4380:
defoamer (Drew Chem. Corp.) e) Acrysol RM 8: non-ionic thickener (Rohm and
Haas Comp.); f) Bayferrox 130 M: red iron oxide pigment (Bayer AG); g)
Millicarb: calcium carbonate (Omya); h) Maincote HG-54: acrylic dispersion
(Rohm and Haas Comp.); i) Texanol. coalescent (Eastman Chem. Prod., Inc.);
k) Di-butylphthalate: plastisizer (Eastman Chem. Prod., Inc.); l) sodium
nitrite: flash rust inhibitor (Fluka); m) Drew T 4310: non-ionic defoamer
(Drew Chem. Corp.)
As fluorescent agents the following maleimides (component 9) obtained from
examples 35, 98, 28, 22, 33, 31, 96, as well as a mixture of
1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one-7 and -8
(obtained according to example 1 of WO 98/33862 are used.
The components 1 to 8 or 1 to 9 respectively are dispersed at 3000 rpm to a
particle size of <15 .mu.m using a high-speed disperser. The compounds l
or la of the present invention are thereby incorporated in a range chosen
from 0.1 to 1% by weight, based on the total solids of the formulation
containing no fluorescent agent (solids content=47% by weight). According
to this, a concentration of 1% b.w. translates to 0.47 g per 100 g paint.
The formulation is completed under reduced speed (100 rpm) by adding the
components 10 to 16 in the given order. Prior to application the pH of the
formulation is adjusted to pH 8-8.5 using a ammonium hydroxide solution
(25%).
The formulations are sprayed onto aluminum panels at a dry film thickness
in the range of from 50 to 55 .mu.m. Once the formulations are cured the
coatings are inspected under an UV-lamp. Defects or voids as a result of
misapplication or artificially applied defects can be easily detected, as
the compounds of the present invention show intense fluorescence only at
the voids. No fluorescence is observed in the absence of the fluorescent
agents.
Example 127
A solvent based white pigmented 2 pack epoxy primer is prepared according
to the following formulation:
Composition parts by wt.
1) Araldit GZ 7071.sup.a) (75% in xylene) 24.2
2) Aerosil R 972.sup.b) 0.5
3) Thixatrol ST.sup.c) 0.2
4) Kronos RN 56.sup.d) 25.0
5) Bayferrox 318M.sup.e) 0.1
6) Micr. Talk AT Extra.sup.f) 15.8
7) Blanc Fixe.sup.g) 14.2
8) Cyclohexanone 8.3
9) Xylene 11.7
10) n-Butanol 10.0
11) fluorescent agent
Subtotal 110.0
12) Hardener HY 815.sup.h) (50% in xylene) 18.2
Total 128.2
solids (wt.- %): 64.8
wherein:
a) Araldit GZ 7071: epoxy resin (Ciba Specialty Chemicals, Inc.); b)
Aerosil R 972: synthetic silica, thickener (Degussa AG); c) Thixatrol ST:
anti-settling agent, thixotropic agent (Kronos Titan GmbH); d) Kronos RN
56: titanium dioxide (Kronos Titan GmbH); e) Bayferrox 318 M: iron oxide
black (Bayer AG); f) Talc AT Extra (Norwegian); g) Blanc Fixe: barium
sulphate (Sachtleben); h) Hardener HY 815: polyamido amine (Ciba Specialty
Chemicals, Inc.)
As fluorescent agents the following maleimides (component 11) obtained from
examples 35, 98, 28, 22, 33, 31, 96, as well as a mixture of
1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one-7 and -8
(obtained according to example 1 of WO 98/33862) are used.
The components 1 to 10 or 1 to 11 respectively are dispersed on a ball mill
or equivalent to a particle size <15 .mu.m. The compounds of the present
invention are thereby incorporated in a range of from 0.1 to 1% b.w. The
amounts are based on the total solids of the formulation containing no
fluorescent agent (solids=64.8% b.w.). According to this an amount of 1%
b.w. corresponds to 0.64 g per 128.2 g paint. Prior to application the
hardener (component 12) is added. For spray application the viscosity is
adjusted using xylene as a solvent.
The formulations are sprayed onto aluminium panels at a dry film thickness
of 70 .mu.m. Once the formulations are cured the coatings are inspected
under a UV-lamp. Defects or voids as a result of misapplication or
artificially applied defects can be easily detected, as the compounds of
the present invention show intense fluorescence at the voids. No
fluorescence is observed in the absence of the fluorescent agents.
Example 128
A 2 pack epoxy primer according to example 127 is prepared thereby
replacing component 4 (Kronos RN 56) by iron oxide red (Bayferrox 318 M).
The resulting red/brownish formulation is made and evaluated as described
in example 127.
Example 129
The inventive maleimides according to formula I are incorporated in a
concentration of 0.5% to 1% (based on the total solids of the formulation
containing no fluorescent agent; solids content=19%) into a commercial
automotive cathodic electrocoat.
During electrodeposition the bath temperature is kept at 28.degree. C.
whilst stirring. The electrocoat is deposited onto steel panels at 250
Volts for 2 minutes. After application the panels are rinsed with
demineralized water and subsequently baked at 180.degree. C. for 25
minutes. The resulting film thickness is 25 .mu.m. Once the formulations
are cured, the coatings are inspected under a UV-lamp. Defects or voids as
a result of misapplication or artificially applied defects can be easily
detected, as the compounds of the present invention show intense
fluorescence at the voids. No fluorescence is observed in the absence of
the fluorescent agents.
Example 130
Example 115 is repeated replacing the light-emitting material and the
cathode with the film co-deposited using
tris-(8-hydroxyquinolinato)aluminum(III) (manufactured by Wako Pure
Chemicals Industries, Ltd.) and the compound of formula XI (ca. 4.0 wt %)
and the cathode co-deposited using magnesium and silver (Mg:Ag, 20:1),
respectively. The co-deposition is done under a depositing condition of
6.665.times.10.sup.-4 Pa (5.0.times.10.sup.-6 Torr) and 320 pm/s (3.2
.ANG./s) for the aluminum complex, 13 pm/s (0.13 .ANG./s) for the compound
of formula XI, 200 pm/s (2.0 .ANG./s) for magnesium and 10 pm/s (0.1
.ANG./s) for silver. For comparison, the device employing the compound of
the complex for light-emitting substance is prepared using the cathode of
Mg:Ag (20:1).
The device the light-emitting layer of which comprises of solely the
aluminum complex indicates green EL emission. The emission maximum is at
520 nm in wavelength. The device the light-emitting layer of which
comprises of the complex and the compound of formula XI exhibits EL
emission whose maximum wavelength is at 620 nm, i.e. an orange red
emission which is different from that of the single component device
above. This suggests that the emission is induced via resonance energy
transfer from the aluminum complex to the compound invented.
The above results demonstrate that the invented compounds are useful for
energy acceptor of Host-Guest type of light-emitting materials.
Example 131
(a) 5.5 g (0.02 mol) of 4-trans-stilbene glyoxylic acid is placed in a
flask containing 2.46 g (22 mmol) of tert.-BuOK and 30 ml of methanol. The
mixture is heated up to reflux for 30 min. Then the methanol is removed to
give the corresponding 4-trans-stilbene glyoxylic acid potassium salt. To
the obtained potassium salt 4.76 g (20 mmol) of 4-trans-stilbene acetic
acid and 30 ml of acetic anhydride are added and heated up to 130.degree.
C. for 2 hours. After cooling to room temperature, acetic anhydride is
removed from the mixture and the product is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 /hexane). 6.5 g (62%) of the
corresponding maleic anhydride are obtained.
(b) A mixture of 4.55 g (10 mmol) of the thus obtained maleic anhydride,
7.1 g (30 mmol) of 2,6-diisopropylaniline and 50 ml of acetic acid is
heated up to 130.degree. C. form eight hours. After the acetic acid is
removed under an atmosphere of reduced pressure, the product is purified
by column chromatography (silica gel, CH.sub.2 Cl.sub.2 /hexane). 5.03 g
(82%) of an orange-red maleimide of the formula XIX are obtained
##STR46##
Example 132
Example 131 is repeated except that cyclohexylamine is used instead of
2,6-diisopropylaniline. An orange solid (72%) of the formula XX is
obtained
##STR47##
Example 133
Example 102 is repeated except that cyclohexylamine is used instead of
2,6-diisopropylaniline. A red solid (68%) of the formula XXI is obtained
##STR48##
Example 134
Example 102 is repeated except that isopropylamine is used instead of
2,6-diisopropylaniline. A red solid (73%) of the formula XXII is obtained
##STR49##
Example 135
Example 102 is repeated except that o-toluidine is used instead of
2,6-diisopropylaniline. A red solid (76%) of the formula XXIII is obtained
##STR50##
Example 136
Example 102 is repeated except that ethyleneamine is used instead of
2,6-diisopropylaniline. A red solid (54%) of the formula XXIV is obtained
##STR51##
Example 137
Example 102 is repeated except that 1,4-diaminocyclohexane is used instead
of 2,6-diisopropylaniline. A red solid (58%) of the formula XXV is
obtained
##STR52##
Example 138
5.35 g (20 mmol) of 9-ethylcarbazole-3-glyoxylic acid is placed in a flask
containing 2.46 g (22 mmol) of tert.-BuOK and 25 ml of methanol. The
mixture is heated up to reflux for 30 min. Then the methanol is removed to
give the corresponding 4-trans-stilbene glyoxylic acid potassium salt. To
the obtained potassium salt 4.76 g (20 mmol) of 4-trans-stilbene acetic
acid and 30 ml of acetic anhydride are added and heated up to 130.degree.
C. for 2 hours. After cooling to room temperature, acetic anhydride is
removed from the mixture and the product is purified by column
chromatography (silica gel, CH.sub.2 Cl.sub.2 /hexane). 7.1 g (73%) of the
corresponding maleic anhydride are obtained.
(b) A mixture of 4.83 g (10 mmol) of the thus obtained maleic anhydride,
7.1 g (30 mmol) of 2,6-diisopropylaniline and 50 ml of acetic acid is
heated up to 130.degree. C. form eight hours. After the acetic acid is
removed under an atmosphere of reduced pressure, the product is purified
by column chromatography (silica gel, CH.sub.2 Cl.sub.2 /hexane). 5.01 g
(78%) of an orange-red maleimide of the formula XXVI are obtained
##STR53##
Example 139
(a) To 24.6 g (0.18 mol) of AlCl.sub.3 in 200 ml of CH.sub.2 Cl.sub.2 a
mixture of 30 g (0.12 mol) of 9-phenyl carbazole and 17.75 g (0.13 mol) of
ethyl chloroglyoxylate in 100 ml of CH.sub.2 Cl.sub.2 is added dropwise at
ice-bath temperature over 1 h. After completion of addition, the mixture
is gradually allowed to room temperature and stirred over night. Then, the
reaction mixture is poured onto ice. The aqueous solution is acidified to
pH 3 with aq. HCl, and the product is extracted with CH.sub.2 Cl.sub.2
afterwards. The extract is dried over anhydrous MgSO.sub.4. The desired
product is purified by Silica gel column chromatography using CH.sub.2
Cl.sub.2 -hexane mixture as eluent. 24.5 g of ethyl
3-(9-phenylcarbazole)glyoxylate are obtained (58%).
(b) 24.5 g (0.07 mol) of ethyl 3-(9-phenylcarbazole)glyoxylate are treated
with 3.6 g (0.09 mol) of NaOH in 75 ml of H.sub.2 O and 75 ml of ethanol
under reflux for 2 h. The mixture is acidified to pH 3 with aq. HCl, and
then extracted with CH.sub.2 Cl.sub.2. After drying, 17.0 g of
3-(9-phenylcarbazole)glyoxylic acid are obtained as a crude product (74%).
This product is used for the next reaction step without further
purification
(c) 3.15 g (0.01 mol) of 3-(9-phenylcarbazole)glyoxylic acid are placed in
a flask containing 1.23 g (0.011 mol) of tert.-BuOK and 30 ml of methanol.
The mixture is heated up to reflux for 30 min. Then the methanol is
removed to give 3-(9-phenylcarbazole)glyoxylic acid potassium salt. To the
obtained potassium salt, 2.37 g (0.01 mol) of 4-trans-stilbene acetic acid
and 30 ml of acetic anhydride are added and heat up to 130.degree. C. for
4 hours. After the reaction mixture is allowed to cool to room
temperature, acetic anhydride is removed and the product is purified by
column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture). 1.1
g (22%) of the corresponding maleic anhydride are obtained.
(d) 1.1 g (2.1 mmol) of this maleic anhydride, 0.63 g (6.3 mmol) of
cyclohexylamine, 10 ml of N,N-dimethylformamide and 30 ml of toluene are
heated up to 130.degree. C. for 6 hours. After the used solvents are
removed under an atmosphere of reduced pressure, the product is purified
by column chromatography (silica gel, CH.sub.2 Cl.sub.2 -hexane mixture).
0.91 g (72%) of an orange-red maleimide XXVII are obtained
##STR54##
Example 140
Example 115 is repeated, except the following light emitting compounds are
employed. The results are summarized in the Table 20.
TABLE 20
Light-Emitting Material EL Emission Peak EL Intensity
Example (Example) wavelength (nm) (cd/m.sup.2)
140 131 589 230
141 132 582 243
142 133 637 400
143 134 659 82
145 136 656 94
146 137 655 164
147 138 618 430
148 139 610 320
Example 149
Example 115 is repeated for EL device preparation using as light emitting
material compound XIX (ex. 131) as an energy donor and Lumogen.RTM.Red 300
(BASF) as an energy acceptor. Table 21 below shows the results.
Examples 150-151
Example 149 is repeated, except the following light energy donors are
employed (see Table 21). The results are summarized in Table 21.
TABLE 21
EL
Emission
Host Guest/Lumogen .RTM. Peak EL
material Red 300 wavelength Intensity
Example (example) concentration [wt.- %] [nm] [cd/m.sup.2 ]
149 107 1 609 522
150 131 2 612 478
151 132 1.8 614 548
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